記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The combination of a cobalt-dioxolene core that exhibits valence tautomerism (VT) with pyridine-3,5-dicarboxylic acid functionalized with chains bearing two, four, or six oxyethylene units led to new complexes ConEGEspy (n = 2, 4, and 6). These complexes commonly form violet crystals of the low-spin (ls)-[Co-III(nEGEspy)(2)(3,6-DTBSQ)(3,6-DTBCat)] (ls-[Co-III], 3,6-DTBSQ = 3,6-di-tert-butyl semiquinonato, 3,6-DTBCat = 3,6-di-tert-butyl catecholato). Interestingly, violet crystals of Co2EGEspy in the ls-[Co-III] transitioned into a green liquid, accompanied by an almost complete VT shift (94 %) to the high-spin (hs)-[Co-II(nEGEspy)(2)(3,6-DTBSQ)(2)] (hs-[Co-II]) upon melting. In contrast, violet crystals of Co4EGEspy and Co6EGEspy in the ls-[Co-III] exhibited partial VT (33 %) and only a 9.3 % VT shift after melting, respectively. These data demonstrate the tunability of the synchronicity of the molecular VT and macroscopic solid-liquid transitions by optimizing the tethered chains, thus establishing a new strategy for coupling bistable molecules with the macroscopic world.

DOI： 10.1002/chem.202103090

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Exploring new types of photochemical reactions is of great interest in the field of synthetic chemistry. Although excited-state hydrogen detachment (ESHD) represents a promising prospective template for additive-free photochemical reactions, applications of ESHD in a synthetic context remains scarce. Herein, we demonstrate the expansion of this photochemical reaction toward oligomerization, disulfidation, and regioselective C(sp2)-H carboxylation of aromatic alcohols, thiols, and amines. In the absence of any radical initiators in tetrahydrofuran upon irradiation with UV light (λ = 280 or 300 nm) under an atmosphere of N2 or CO2, thiols and catechol afforded disulfides and oligomers, respectively, as main products. Especially, the photochemical disulfidation proceeded highly selectively with the NMR and quantum yields of up to 69 and 0.46%, respectively. In stark contrast, the photolysis of phenylenediamines and aminophenols results in photocarboxylation in the presence of CO2 (1 atm). p-Aminophenol was quantitatively carboxylated by photolysis for 17 h with a quantum yield of 0.45%. Furthermore, the photocarboxylation of phenylenediamines and aminophenols proceeds in a highly selective fashion on the aromatic C(sp2)-H bond next to a functional group, which is directed by the site-selective ESHD of the functional groups for the formation of aminyl and hydroxyl radicals.

DOI： 10.1021/acs.joc.0c02456

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

We previously reported that a tris-(o-phenylenediamine) iron(ii) complex promotes photochemical H2 generation and C-H carboxylation of o-phenylenediamine without any additives under N2 and CO2 atmospheres, respectively, in tetrahydrofuran at room temperature. Herein, the key mechanistic process, namely, excited-state hydrogen detachment from the o-phenylendiamine moiety, is demonstrated under an N2 atmosphere.

DOI： 10.1039/d0cc06219g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Zeolites are usually synthesized by hydrothermal reactions using monomeric or polymeric Al- and Si-containing precursors, whereas simple and direct routes for the rational synthesis of zeolites remain elusive. In this work, we demonstrate the synthesis of the two zeolites L (LTL type) and W (MER type) from a single molecular precursor (MP), (PyH)[Al{Ph2Si(OSiPh2O)(2)}(2)] (AlSi6 ; PyH = pyridinium cation), under hydrothermal conditions using KOH as the only additive. Under acidic conditions, the heptanuclear structure of AlSi6 is hydrolyzed without cleavage of the Si-Ph bonds, while the hydrothermal reaction under basic conditions allows the crystallization of zeolites under concomitant Si-Ph cleavage. X-ray diffraction and scanning electron microscopy studies revealed that zeolite L, which exhibits a cylindrical morphology, was produced selectively by hydrothermal treatment of AlSi6 at 160-200 degrees C in the presence of KOH (3 eq.). In contrast, increasing the amount of KOH (from 6 to 12 eq.) resulted in the formation of zeolite W with a twin-ball morphology. The specific surface area and Si/Al ratios of the synthesized zeolites L and W are comparable to those previously reported. These experimental results suggest promising potential of structurally and compositionally well-defined MPs, including even those with organic functional groups, for the construction of zeolites.

DOI： 10.1039/d0ce00546k

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs-[6R]2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls-[0R]2+) formation by O2 oxidation of hs-[6R]2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls-[0R][PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls-[2R][PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls-[4R][PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.

DOI： 10.1002/chem.202001873

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.201900172

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41598-018-33060-3

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その他リンク： http://www.nature.com/articles/s41598-018-33060-3

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

Methylation of the molybdenum sulfide cluster unit [Mo6S8(PEt3)6] (1) with CH3OTf resulted in the formation of mono- and dimethylated cluster units, [Mo6S8–x(SCH3)x(PEt3)6]OTf·yCH2Cl2 {[2]OTf·0.5CH2Cl2 (x = 1, y = 0.5) and [3]OTf·CH2Cl2 (x = 2, y = 1)}. Structural and electrochemical investigations revealed that the methylation of the µ3-S ligand(s) induced a characteristic structural distortion of the [Mo6S8] cluster core and enhanced its ability to accept multiple electrons.

DOI： 10.1002/ejic.201800587

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.201706006

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The reaction of N,N'-bis(diisopropylphosphoniumacetyl)-o-phenylenediamide dibromide (H4L center dot 2Br) with Ni-II[ClO4]center dot 6H(2)O in the presence of Et3N resulted in the formation of N, N'-bis(diisopropylphosphinoacetyl)-o-phenylenediamidate nickel(II) ([Ni-II(L)]). The single-crystal X-ray diffraction analysis of [Ni-II(L)] revealed that each pair of N and P atoms in L2- coordinates in a tetradentate fashion to afford a distorted square-planar Ni-II amide complex. On the other hand, N, N'-bis(diisopropylphosphinoacetyl)- o-phenylenediamide copper(I) bromide ([Cu-I(H2L)Br]) was isolated by the reaction of H4L center dot 2Br with [Cu-I(MeCN)(4)][PF6] in the presence of Et3N. The structural analysis revealed that the two P atoms in H2L coordinate in a bidentate fashion to afford a trigonal-planar Cu-I complex, in which the amide moieties remain in free form. Complex [Ni-II(L)] showed reversible deprotonation processes on the amidate ligand (L2-), whereas the protonated state of the N atoms of the amide ligand (H2L) in [Cu-I(H2L)Br] was maintained, even in the presence of excess Et3N, suggesting substantial stability for the protonated state.

DOI： 10.1002/ejic.201700433

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201701613

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その他リンク： http://orcid.org/0000-0002-6932-9758

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

The coordinative interactions of o-phenylenediamine and alkali or alkaline earth metals like Li+, Na+, Mg2+, or Ca2+, were investigated by X-ray structural analyses and IR, UV-vis, and (HNMR)-H-1 spectroscopies. These studies revealed that the coordinative interactions of o-phenylenediamine with metal ions through amino groups depend on the ratio of the charge and the ionic radius of the metal ions both in the solid state and in THF solution.

DOI： 10.1246/cl.160997

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：NATURE PUBLISHING GROUP  

Dehydrogenation of anhydrous methanol is of great importance, given its ubiquity as an intermediate for the production of a large number of industrial chemicals. Since dehydrogenation of methanol is an endothermic reaction, heterogeneous or homogeneous precious-metal-based catalysts and high temperatures are usually required for this reaction to proceed. Here we report the photochemical dehydrogenation of anhydrous methanol at room temperature catalysed by o-aminophenol (apH(2)), o-aminophenolate (apH(-)) and the non-precious metal complex trans-[Fe-II(apH)(2)(MeOH)(2)]. Under excitation at 289 +/- 10 nm and in the absence of additional photosensitizers, these photocatalysts generate hydrogen and formaldehyde from anhydrous methanol with external quantum yields of 2.9 +/- 0.15%, 3.7 +/- 0.19% and 4.8 +/- 0.24%, respectively, which are the highest values reported so far to the best of our knowledge. Mechanistic investigations reveal that the photo-induced formation of hydrogen radicals triggers the reaction.

DOI： 10.1038/ncomms12333

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-Blackwell  

A novel platinum(II)-diimine complex, [Pt(CN)(2)(H(2)dcphen)] (1; H(2)dcphen=4,7-dicarboxy-1,10- phenanthroline), was synthesized and its vapochromic shape-memory behavior was evaluated. The as-synthesized amorphous purple solid, [Pt(CN)(2)(H(2)dcphen)]2H(2)O (1P), exhibited vapochromic behavior in the presence of alcoholic vapors through transformation to a red, crystalline, porous, vapor-adsorbed form, 1Rvapor. The obtained 1Rvapor complex released the adsorbed vapors upon heating without collapse of the porous structure. The vaporfree, porous 1Ropen could detect water or n-hexane vapor, although these vapors could not induce 1P-to-1Rvapor transformation, and 1Ropen could easily be converted to the initial 1P by manual grinding. These results indicate that 1 is a new shape-memory material that functions through formation and collapse of the porous framework with an emission change upon vapor-adsorption and grinding; this enables it to exhibit vapor history and ON-OFF switching sensing functions.

DOI： 10.1002/chem.201503247

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Chemical one-electron oxidation of [Pt-II(3,5-DTBCat)(DTBbpy)] (1) (3,5-DTBCat = 3,5-di-tert-butyl catecholato, DTBbpy = 4,4'-di-tert-butyl-2,2'-bipyridine) afforded the corresponding paramagnetic complex, [Pt-II(3,5-DTBSQ)(DTBbpy)]+PF6- (1(PF6)), as a result of ligand-centred oxidation. While complex 1 is relatively stable in common organic solvents, the present study demonstrates that cationic [1](+) is subject to an unprecedented solvent-induced disproportionation in highly polar solvents such as DMSO and DMF, which results in the formation of 1 and a free benzoquinone.

DOI： 10.1039/c6dt00487c

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20140208

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記述言語：日本語   出版者・発行元：日本液晶学会  

Redox-active liquid crystals that have both liquid crystalline and redox properties are expected to give new and attractive electronic devises controlled by electrochemical methods at ambient conditions. We have reported the design and properties of Pt(II) metallomegens possessing redox-active catecholato or benzenedithiolato and long alkyl chain-substituted bipyridine ligands. Especially, metallomesogen possessing 3,5-t-butylcatecholato shows direct electrochemical redox responses and electrochemically -induced transformation between columnar liquid crystal and isotropic ionic liquid phases. In this work, the effects of coordinating atoms, the position of substituents, temperature, and electrolytes on electrochemical property of metallomesogens will be presented.

DOI： 10.11538/ekitou.2015.0__PB26

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.inorgchem.5b00578

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c5dt01963j

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ic5021302

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

The reaction of tetraethyl [2,3-dihydroxy-1,4-phenylenebis-(methylene)]bisphosphonate (Et4LH2) with [PtCl2(DTBbPY)] (DTBbpy: 4,4'-di-tert-butyl-2,2'-bipyridine) afforded [Pt(Me4L)-(DTBbpY)] (1), [Pt(Bn4L-)(DTBbPY)] (2), Na-2[Pt(Me2L)-(DTBbpy)] (3), and [Pt(H4L)(DTBbpy)] (4) with tetramethyl-, tetrabenzyl-, half-protected, and fully-deprotected groups under different reaction conditions. The introduction of phosphonatomethyl groups at the 3,6-position of a redox-active catecholato unit led to slight shifts in charge-transfer bands and catecholato-centered redox processes in solution. The presence of deprotonated anchors in 3 resulted in the immobilization of the complex onto an indium-doped tin oxide electrode, demonstrating a well-defined redox response from the tethered complex.

DOI： 10.1246/cl.140235

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

A new porous coordination polymer (PCP), formulated as {[La-2(III)(mu(3)-OH)(CH3COO)(2)(H2O)][Cu-I(dmdcbpy)(2)]center dot 9H(2)O} (La2Cu center dot 9H(2)O; H(2)dmdcbpy: 6,6'-dimethyl-5,5'-dicarboxy-2,2'bipyridine), was synthesized and characterized by X-ray diffraction and vapor-adsorption isotherms. The porous framework of La2Cu consists of a 3-D coordination network of the Cu(I)-metalloligand and the tetranuclear La-4 cluster {La-4(mu(3)-OH)(2)(CH3COO)(4)(H2O)(2)}. La2Cu exhibits reversible guest adsorption desorption for various vapors, with reversible structural transformations.

DOI： 10.1246/cl.140249

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

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記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ACS  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：RSC  

DOI： 10.1039/c4dt00316k

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ACS  

DOI： 10.1021/ic402104q

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記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：RSC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ACS  

The combination of o-phenylenediamine (opda), which possesses two proton- and electron-pooling capability, with Fe(II) leads to the photochemical hydrogen-evolution reaction (HER) in THF at room temperature without addition of photosensitizers. From the THF solution, the tris(o-phenylenediamine) iron(II) complex, [FeII(opda)3](ClO4)2 (1), was isolated as a photoactive species, while the deprotonated oxidized species was characterized by X-ray crystallographic analysis, electrospray ionization mass spectrometry, and UV-vis NIR spectra. Furthermore, the HER is photocatalyzed by hydroquinone, which serves as a H+/e- donor. The present work demonstrates that the use of a metal-bound aromatic amine as a H+/e- pooler opens an alternative strategy for designing nonprecious-metal-based molecular photochemical H2 production/storage materials. © 2013 American Chemical Society.

DOI： 10.1021/ja4025116

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

The presence of lone pairs on the Pt and S atoms of [Pt(Bdt)(DTBbpy)] (1) (Bdt = 1,2-benzenedithiolato and DTBbpy = 4,4'-di-tert-butyl-2,2'-bipyridine) and [Pt (Bdt) (C13bpy)] (2) (C13bpy = 4,4'-ditridecyl-2,2'-bipyridine) led to selective dative bond formation with Cd(II). Complexes 1 and 2 show no binding interaction with Zn(II), while they bind selectively with Cd(II) to give a twisted trinuclear complex, [Cd{Pt(Bdt)(DTBbpy)}(2)(ClO4)(H2O)](ClO4) (3), and a shuttlecock-shaped tetranuclear complex, [Cd{Pt(Bdt)(C13bpy)}(3)(H2O)](ClO4)(2)center dot CH2Cl2 (4), respectively, depending upon the alkyl groups substituted on the 2,2'-bipyridine. The two platinum moieties in 3 are connected to the seven-coordinated Cd atom through Pt -> Cd (2.7331(7) and 2.7936(7) angstrom) and S -> Cd (2.690(3), 2.940(3), and 3.067(3) angstrom) dative bonds, while the three moieties in 4 are connected to the tetrahedral Cd atom only by S -> Cd (2.552(4) angstrom) dative bonds. These structural variations found in 3 and 4 are caused not only by steric hindrance of the t-Bu groups but also by the microsegregation effect derived from the tridecyl chains. The three platinum moieties in 4 align so as to form a parallel orientation of their dipole moments, in contrast to the twisted arrangement found in 3. The dative bonds formed in 3 and 4 are commonly stable in the solid state and in less coordinative solvents such as dichloromethane, while dissociation behavior of platinum moieties with Cd(II) was observed in more coordinative THF. UV-vis and NMR spectroscopy unsealed the characteristic association/dissociation properties depending on the coordination abilities of solvents. Finally, the present study revealed that the formation of dative bonds between the platinum moieties with Cd(II) plays important roles not only in stabilizing the ground states, which leads to blue shifts in both absorption and emission energies, but also in electronic interactions between the moieties, which are revealed by electrochemical studies.

DOI： 10.1021/ic302352k

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その他リンク： http://orcid.org/0000-0002-6932-9758

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ACS  

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Heterodinuclear complexes, syn-[MPt(mu-pyt)(2)(bpy)(2)](n+) (syn-[MPt], M = Pd2+, Au3+, Hpyt = pyridine-2-thiol, bpy = 2,2'-bipyridine), were synthesized as a selective geometrical isomer by stepwise complexation. X-ray analyses of the hexafluorophosphate salts of these complexes proved their dinuclear structures with short M...Pt distances (2.9084(4) angstrom for syn-[PdPt] and 2.9071(4) angstrom for syn-[AuPt]), similar to the homodinuclear complex (2.9292(2) angstrom for syn-[PtPt]). In the syn-[PdPt] crystal, two dinuclear motifs are arranged closely in a head-to-head manner with a short Pt...Pt distance (3.3757(3) angstrom), forming a dimer-of-dimer structure as in the case of syn-[PtPt], whereas the corresponding crystal of syn-[AuPt] has a discrete arrangement of the dinuclear motifs. By the isomerisation of syn-[PdPt], anti-[PdPt] with equivalent environments of the Pd2+ and Pt2+ ions was also obtained successfully. Syn-[PdPt](PF6)(2) exhibits vapochromic behaviour based on the absorption/desorption of CH3CN vapour, similar to that observed for syn-[PtPt](PF6)(2). The reversible structural transformations induced by the uptake and release of CH3CN molecules were investigated by powder and single-crystal X-ray diffraction studies. These revealed that the vapochromic behaviour was based on the interconversion between two phases, the dimer-of-dimer structure with a short Pt. Pt distance and a p-p stacked arrangement with no Pt. Pt intermolecular interaction. The introduction of the heterometal ions enabled control of the colour region: orange. red for syn-[PdPt] vs. light red. dark red for syn-[PtPt], reflecting the weaker metal-metal interaction between Pd2+ and Pt2+ ions in the dinuclear motif. In addition, these complexes were found to exhibit mechanochromic behaviour based on a crystal-to-amorphous transformation upon grinding, and the reconstruction of the crystal structures by vapour sorption.

DOI： 10.1039/c3dt33100h

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その他リンク： http://orcid.org/0000-0002-6932-9758

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

We synthesized a novel Pt(II)-diimine complex with a typical ambidentate thiocyanato ligand, [Pt(thiocyanato)(2)(H(2)dcbpy)] (1; H(2)dcbpy =4,4'-dicarboxy-2,2'-bipyridine), and found that the complex 1 exhibits unique linkage isomerizations with drastic color and luminescence changes driven by exposure to volatile organic chemical (VOC) vapors in the solid state. Reaction between [PtCl2(H(2)dcbpy)] and KSCN in aqueous solution at 0 degrees C enabled successful isolation of an isomer with the S-coordinated thiocyanato ligand, [Pt(SCN)(2)(H(2)dcbpy)] (1SS center dot H2O), as a nonluminescent orange solid. Interestingly, 1SS center dot H2O was isomerized completely to one isomer with the N-coordinated isothiocyanato ligand, [Pt(NCS)(2)(H(2)dcbpy)] (1NN center dot 3DMF) by exposure to DMF vapor, and this isomerization was accompanied by significant color and luminescence changes from nonluminescent orange to luminescent red. IR spectroscopy and thermogravimetric analysis revealed that adsorption of the DMF vapor and transformation of the hydrogen-bonded structure both played important roles in this vapor-induced linkage isomerization. Another isomer containing both S- and N-coordinated thiocyanato ligands, [Pt(SCN)(NCS)(H(2)dcbpy)] (1SN), was obtained as a nonluminescent yellow solid simply by exposure of 1SS center dot H2O to acetone vapor at room temperature, and about 80% of 1SS center dot H2O was found to be converted to 1SN. In the solution state, each isomer changed gradually to an isomeric mixture, but pure 1SS was regenerated by UV light irradiation (lambda(irr) = 300 nm) of an MeOH solution of the mixture. In the crystal structure of 1SN, the complex molecules were hydrogen-bonded to each other through the carboxyl groups of the H(2)dcbpy ligand and the N site of the thiocyanato ligand, whereas the 1NN molecules in the 1NN.4DMF crystal were hydrogen-bonded to the solvated DMF molecules. Competition of the hydrogen-bonding ability among the carboxyl groups of the H(2)dcbpy ligand, N and S atoms of the thiocyanato ligand, and the vapor molecule was found to be one of the most important factors controlling linkage isomerization behavior in the solid state. This unique linkage isomerization controlled by vapor can provide an outstanding vapochromic system as well as a new molecular switching function driven by vapor molecules.

DOI： 10.1021/ic202734f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The redox-active fac-[Mo-V(mp)(3)](-) (mp: o-mercaptophenolato) bearing asymmetric O- and S-cation binding sites can bind with several kinds of metal ions such as Na+, Mn-II, Fe-II, Co-II, Ni-II, and Cu-I. The fac-[Mo-V(mp)(3)](-) metalloligand coordinates to Na+ to form the contact ion pair {Na+(THF)(3)[fac-Mo-V(mp)(3)]} (1), while a separated ion pair, n-Bu4N[fac-Mo-V(mp)(3)] (2), is obtained by exchanging Na+ with n-Bu4N+. In the presence of asymmetric binding-sites, the metalloligand reacts with (MnCl2)-Cl-II center dot 4H(2)O, (FeCl2)-Cl-II center dot 4H(2)O, (CoCl2)-Cl-II center dot 6H(2)O, and (NiCl2)-Cl-II center dot 6H(2)O to afford UV-vis-NIR spectra, indicating binding of these guest metal cations. Especially, for the cases of the MnII and CoII products, trinuclear complexes, {M(H2O)(MeOH)-[ fac-Mo-V(mp)(3)](2)}center dot 1.5CH(2)Cl(2) (3.1.5CH(2)Cl(2) (M = Mn-II), 4.1.5CH(2)Cl(2) (M = Co-II)), are successfully isolated and structurally characterized where the M are selectively bound to the hard O-binding sites of the fac-[Mo-V(mp)(3)](-). On the other hand, a coordination polymer, {Cu-I(CH3CN)[mer-MoV(mp)(3)]}(n) (5), is obtained by the reaction of fac-[Mo-V(mp)(3)]-with [Cu-I(CH3CN)(4)]ClO4. In sharp contrast to the cases of 1, 3.1.5CH(2)Cl(2), and 4.1.5CH(2)Cl(2), the Cu-I in 5 are selectively bound to the soft S-binding sites, where each CuI is shared by two [MoV(mp) 3]-with bidentate or monodentate coordination modes. The second notable feature of 5 is found in the geometric change of the [MoV(mp) 3]-, where the original fac-form of 1 is isomerized to the mer-[Mo-V(mp)(3)](-) in 5, which was structurally and spectroscopically characterized for the first time. Such isomerization demonstrates the structural flexibility of the [Mo-V(mp)(3)](-). Spectroscopic studies strongly indicate that the association/dissociation between the guest metal ions and metalloligand can be modulated by solvent polarity. Furthermore, it was also found that such association/dissociation features are significantly influenced by coexisting anions such as ClO4- or B(C6F5)(4)(-). This suggests that coordination bonds between the guest metal ions and metalloligand are not too static, but are sufficiently moderate to be responsive to external environments. Moreover, electrochemical data of 1 and 3.1.5CH(2)Cl(2) demonstrated that guest metal ion binding led to enhance electron-accepting properties of the metalloligand. Our results illustrate the use of a redox-active chalcogenolato complex with a simple mononuclear structure as a multifunctional metalloligand that is responsive to chemical and electrochemical stimuli.

DOI： 10.1039/c2dt30178d

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Reactions of a Pt(II)-diimine-based metalloligand Na-2[Pt(CN)(2)(4,4'-dcbpy)] (4,4'-H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) with alkaline-earth metal salts Mg(NO3)(2)center dot 6H(2)O, CaCl2, SrCl2 center dot 6H(2)O, and BaBr2 center dot 2H(2)O in aqueous solution gave luminescent complexes formulated as [Mg(H2O)(5)][ Pt(CN)(2)(4,4'-dcbpy)]center dot 4H(2)O (MgPt-4 center dot 9H(2)O), {[Ca(H2O)(3)][Pt(CN)(2)(4,4'-dcbpy)]center dot 3H(2)O}(infinity) (CaPt-4 center dot 6H(2)O), {[Sr(H2O)(2)][Pt(CN)(2)(4,4'-dcbpy)]center dot H2O}(infinity) (SrPt-4 center dot 3H(2)O), and {[Ba(H2O)(2)][ Pt(CN)(2)(4,4'-dcbpy)]center dot 3H(2)O}(infinity) (BaPt-4 center dot 5H(2)O), respectively. The crystal structures of all MPt-4 complexes were determined by X-ray crystallography. In these structures, the alkaline-earth metal ions are commonly coordinated to the carboxyl groups of the [Pt(CN)(2)(4,4'-dcbpy)](2-) metalloligand. In the case of MgPt-4 center dot 9H(2)O, the Mg(II) ion is bound by five water molecules and one oxygen atom of a carboxyl group to form a neutral complex molecule [Mg(H2O) 5][Pt(CN)(2)(4,4'-dcbpy)]. In contrast, the alkaline-earth metal ion and metalloligand form two-dimensional (CaPt-4 center dot 6H(2)O) and three-dimensional (SrPt-4 center dot 3H(2)O and BaPt-4 center dot 5H(2)O) coordination networks, respectively. All fully hydrated complexes exhibited a strong phosphorescence from the triplet pi-pi* transition state. Luminescence spectroscopy revealed that MgPt-4 center dot 9H(2)O exhibited interesting multichromic (i.e., thermo-, mechano-, and vapochromic) luminescence, whereas CaPt-4 center dot 6H(2)O showed only thermochromic luminescence. The other two complexes did not exhibit any chromic behaviour. Combination analysis of powder X-ray diffraction, thermogravimetry, and IR spectroscopy suggests that the dimensionality of the coordination network contributes considerably to both the structural flexibility and luminescence properties; that is, the low-dimensional flexible coordination network formed in MPt-4 complexes with smaller alkaline-earth metal ions enables a structural rearrangement induced by thermal and mechanical stimuli and vapour adsorption, resulting in the observed multichromic behaviour.

DOI： 10.1039/c1dt11155h

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Dinuclear complexes [{Pt(trpy)}(2)(L)](PF6)(2) (trpy = 2,2': 6',2 ''-terpyridine, L = 2-octylthio-1,3,5-triazine4,6- dithiolate ion (1), L = 2-octadecylthio-1,3,5-triazine-4,6-dithiolate ion (2), L = 2-di-n-butylamino1,3,5- triazine-4,6-dithiolate ion (3)) and a trinuclear complex [{Pt(trpy)}(3)(L)](PF6)(3) (L = 1,3,5-triazine2,4,6- trithiolate ion (4)) have been synthesized and characterized. The single crystal X-ray analysis revealed that the two {Pt(trpy)}(2+) fragments in 1 and 3 adopt a syn-configuration. The Pt...Pt distances are around 4.3 angstrom, suggesting no intramolecular Pt...Pt interactions. Complexes 1-4 in acetonitrile show broad absorption bands at around 470 nm, assigned to mainly the ligand-to-ligand charge transfer ((LLCT)-L-1) from triazine thiolates to trpy based on the comparison to the related complexes and the density functional theory (DFT) calculations. The red luminescence of 1-4 in acetonitrile is attributable to emission predominantly from (LLCT)-L-3. Cyclic voltammograms of 1-3 exhibit four redox couples from -2.0 V to 0 V vs. Ag/AgCl. The two consecutive processes at around -0.70 V are assigned to the sequential reduction of two trpy ligands. This assignment was further supported by the observation of the anion radical of trpy in spectroelectrochemical experiments. The splitting of the redox potentials of two trpy ligands evidences the moderate electronic coupling interactions mediated by the triazine dithiolate bridges. Complex 2 formed a transparent red gel in CH3CN, whereas 4 produced a gel-like solid in the mixtures of CH3CN and other solvents. The interactions dominating the aggregative behaviours have been discussed based on the results of electronic absorption and emission spectroscopy.

DOI： 10.1039/c2dt30997a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

DOI： 10.1246/cl.2011.1335

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

We describe the novel synthesis of a bis(hydrazone)iron(B) complex in protonated [Fe(Hpbph)(2)]Cl-2 (1) and deprotonated [Fe(pbph)(2)] (2) forms and several hydrogen-bonded proton-transfer (HBPT) assemblies having different dimensionalities of hydrogen-bonded network structures, [Fe(Hpbph)2] (CA)center dot 2CH(3)OH (3), [Fe(Hpbph)(2)](HCA)(2)center dot 2THF (4), and [Fe(Hpbph)(2)](CA)(H(2)CA)(2)center dot 2CH(3)CN (5) (Hpbph = 2-(diphenylphosphino)benzaldehyde-2-pyridylhydrazone), consisting of a deprotonated Fe(II)-hydrazone complex (2) as a proton acceptor (A) and chloranilic acid (H2CA) as a proton donor (D). The deprotonated complex 2 exhibited two-step reversible protonation reactions to form the double-protonated form 1, and the acid-dissociation constants were determined to be 7.6 and 10.3 in methanol solution. Utilizing this proton-accepting ability of 2, we succeeded in synthesizing HBPT assemblies 3, 4, and 5 from the reactions in CH3OH, THF, and CH3CN, respectively, with the same D/A ratio of H(2)CA/[Fe(pbph)(2)] = 10:1. These assemblies were found to have one-dimensional (1-D), two-dimensional (2-D), and three-dimensional (3-D) hydrogen-bonded networks with D/A ratios of 1:1, 2:1, and 3:1 for 3, 4, and 5, respectively. In 3, a 1-D hydrogen-bonded chain composed of the alternate arrangement of [Fe(Hpbph)(2)](2+) and CA(2-), {center dot center dot center dot[Fe(Hpbph)(2)](2+)center dot center dot center dot CA(2-)center dot center dot center dot}(infinity), was surrounded by solvated methanol molecules to form isolated 1-D hydrogen-bonded chains. In the HBPT assembly 4, a 2-D hydrogen-bonded sheet was formed from two types of hydrogen-bonded chains, {center dot center dot center dot[Fe(Hpbph)(2)](2+)center dot center dot center dot HCA(-)center dot center dot center dot HCA(-)center dot center dot center dot}(infinity) and {center dot center dot center dot HCA(-)center dot center dot center dot HCA(-)center dot center dot center dot}(infinity), and solvated THF molecules did not form any hydrogen bonds. In 5, two orthogonal hydrogen-bonded chains constructed from the neutral chloranilic acid molecules, {center dot center dot center dot CA2(-)center dot center dot center dot 2(H(2)CA)center dot center dot center dot}(infinity), were formed in addition to the 1-D hydrogen-bonded chain similar to that in 3, resulting in the formation of a rigid 3-D hydrogen-bonded network structure. By controlling the dimensionality of the hydrogen bond network, we found that the 2-D HBPT assembly 4 is sufficiently flexible to exhibit interesting vapochromic behavior in response to various organic vapors.

DOI： 10.1021/ic2008396

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Liquid crystalline (LC) platinum(II) complexes with 1,2-thiophenolato and 1,2-benzendithiolato have been newly synthesized and investigated by spectroscopy together with the catecholato analogue. The variations in coordinating atoms (O or S or O/S mixed) lead to significant modulation in electrochemical properties in solution and absorption and emission properties of the complexes both in solution media and in the condensed phases. The asymmetric, polar mesogens/chromophores consisting of Pt(II), redox-active ligands, and alkyl-substituted bipyridine commonly play important roles not only in stabilizing the columnar LC phases, but also in fluctuations of the ground state energies. A key finding of the present work is the chromic properties of LC complexes induced by the interplay of self-association of the mesogens/chromophores and their fluctuating properties.

DOI： 10.1021/ic102123n

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic102070c

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

We synthesized new porous coordination polymers (PCPs) {Ln(III)[Co(III)(dcbpy)(3)]center dot nH(2)O} (Ln = Nd(3+), Gd(3+); H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and characterized them by X-ray diffraction and vapor-adsorption measurements. These three Ln-Co-based PCPs have similar rock-salt types and highly symmetrical porous structure and show a reversible structural collapse regeneration accompanied by water-vapor desorption adsorption. Similar structural regeneration was also observed for the Gd-Co PCP upon exposure to MeOH and CH(3)CN vapors, whereas the remaining two PCPs barely responded to organic vapors.

DOI： 10.1021/ic102361d

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

A series of cyclometalated dinuclear platinum(II) complexes bridged by pyridine-2-thiolate (pyt) ions, [Pt-2(L)(2)-(pyt)(2)] (HL = 2-(p-tolyl)pyridine (Hptpy), 2-(2-thienyl)pyridine (Hthpy), or benzo[h]quinoline (Hbzqn)), as well as their two-electron-oxidized dinuclear platinum(III) complexes, [Pt2Cl2(L)(2)(pyt)(2)], have been synthesized and characterized. The structures and luminescence properties have been investigated by comparing them with those of the corresponding 2-phenylpyridinato (ppy) complex. All divalent complexes have similar dinuclear frameworks, with short Pt center dot center dot center dot Pt distances (ca. 2.85 angstrom), and exhibit similar intense luminescence from the triplet metal metal-to-ligand charge-transfer ((MMLCT)-M-3) state in glassy solutions. However, they provide different luminescence features reflecting their dynamic behaviors in fluid solutions and their intermolecular interactions in the solid state. [Pt-2(bzqn)(2)(pyt)(2)] containing fused aromatic rings exhibits the most sensitive features to the environment, i.e., it shows the most red-shifted luminescence spectrum in the solid state due to the intermolecular pi-pi interaction. However, in fluid solution, it provides very weak luminescence based on a rapid nonradiative deactivation mainly caused by the fluctuation of the intramolecular pi-pi repulsion between the ligands. [Pt-2(Ptpy)(2)(pyt)(2)], on the other hand, is the most stable luminophore, which always exhibits intense luminescence with an almost constant emission maximum independent of its temperature and state.

DOI： 10.1246/bcsj.20100304

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

We synthesized a thiosemicarbazone-functionalized flavin (Fl-(H) TSC: 2-[2-(3,4-dihydro-7,8-dimethyl-2,4-dioxobenzo[g]pteridin-10(2H)-yl)ethylidene]-hydrazinecarbothioamide) and its Pt(II) complex [Pt(Fl-TSC)(2)], and characterized it using X-ray diffraction, UV-visible absorption and luminescence spectroscopy. X-ray structural analysis for [Pt(Fl-TSC)(2)] revealed that the structure of the isoalloxazine part was almost the same as that in lumiflavin (7,8,10-trimethylisoalloxazine), and the thiosemicarbazone moiety acted as a bidentate ligand to form a PtS2N2 planar conformation. UV-visible absorption and luminescence spectra of these compounds were very similar to those of riboflavin, but the emission intensity and the lifetime decreased considerably. Theoretical calculations suggested that the charge-separated state (Fl(center dot-)-TSC center dot+) contributed to the faster quenching from the (1)pi-pi* emission state.

DOI： 10.1039/c0dt01139h

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Four new bimetallic coordination polymers (CPs), {M[Pt(CN)(2)(5,5'-dcbpy)]center dot 4H(2)O}(n) (M = Mg(2+), Ca(2+), Sr(2+), Ba(2+); 5,5'-H(2)dcbpy = 5,5'-dicarboxy-2,2'-bipyridine) were synthesized using four alkaline-earth metal ions and a Pt(II)-diimine metalloligand [Pt(CN)(2)(5,5'-H(2)dcbpy)]. All four CPs are isomorphous with the Zn complex, {Zn[Pt(CN)(2)(5,5'-dcbpy)]center dot 4H(2)O}(n), which exhibits effective metallophilic interactions between Pt(II) ions. These CPs exhibited colourful thermochromic behaviour and solid-state solvatochromic-like behaviours when suspended in various solvents. Thermogravimetric analysis and vapour-adsorption measurements revealed that the CPs can reversibly adsorb water and MeOH vapours. The emission energy of the triplet metal-metal-to-ligand charge-transfer ((3)MMLCT) state varied markedly upon guest adsorption/desorption. The chromic and vapour-adsorption properties of these CPs depend strongly on the cross-linking M(2+) ions.

DOI： 10.1039/c1dt10518c

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

A new series of substituted hydrazone complexes, [Cu(Hpbph)I] (1), [Cu(Hpbph)PPh3]PF6 (2-PF6), [NiCl-(Hpbph)]Cl (3-Cl), [PtCl(Hpbph)]ClO4 (4-ClO4), and [PtCl(pbph)] (4b) (Hpbph = 2-(diphenylphosphino)benzaldehyde 2-pyridylhydrazone) have been synthesized and characterized. X-ray crystallography revealed that the copper(1) complexes adopt pseudo-tetrahedral geometry, while the nickel(II) and platinum(II) complexes provide square-planar forms. All the complexes exhibit distinct color changes on the basis of the deprotonation/protonation on the ligand although their acid/base behaviors are largely different. The acidity constants (pK(a)) in methanol were determined to be 11.4 (1), 12.5 (2), 7.7 (3), and 6.7 (4). The results indicate that the dissociation of the proton on the ligand strongly depends on the ligand deformation controlled by the coordination geometry of the complexes and ancillary ligands also somewhat affect the acidity.

DOI： 10.1246/bcsj.20100065

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Functionalization of a cobalt/dioxolene complex with branched, asymmetric alkyl chains promotes non-cooperative and cooperative valence tautomerisms synchronized with thermodynamically favoured crystal-to-melt and kinetically generated glass-to-melt phase transitions, respectively, depending on the degree of crystallinity.

DOI： 10.1039/c001568g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Mineral oil microdroplets containing the model antioxidant N,N-didodecyl-N',N'-dietliyl-phenylene-diamine (DDPD) are immobilized into a 100 x 100 pore-array (ca. 10 mu m individual pore diameter, 100 mu m pitch) in a boron-doped diamond electrode surface. The robust diamond surface allows pore filling, cleaning, and reuse without damage to the electrode surface. The electrode is immersed into aqueous electrolyte media, and voltammetric responses 1 or the oxidation of DDPD are obtained. In order to further improve the current responses, 20 wt% of carbon nanofibers are co-deposited with the oil into the pore array. Voltammetric signals are consistent with the oxidation of DDPD and the associated transfer of perchlorate anions (in aqueous 0.1 M NaClO(4)) or the transfer of protons (in aqueous 0.1 M HClO(4)). From the magnitude of the current response, the DDPD content in the mineral oil can be determined down to less than 1 wt% levels. Perhaps surprisingly, the reversible (or midpoint) potential for the DDPD oxidation in mineral oil (when immersed in 0.1 NaClO(4)) is shown to be concentration-dependent and to shift to more positive potential values for more dilute DDPD in mineral oil solutions. An extraction mechanism and the formation of a separate organic product phase are proposed to explain this behavior.

DOI： 10.1002/elan.200904590

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Japan Society of Coordination Chemistry  

The present contribution reviews the synthesis and properties of complexes including redox-active dioxolene ligands as well as its analogues, diiminosemiquinonato, and dithiolene ligands. This review first summarizes the structural and electronic features of new molecular complexes as a building block for constructing electronically labile molecular assemblies. Ligand-based mixed valence (LBMV) state has been realized both in mononuclear chromium and pentanuclear cobalt complexes. Second topic will be on the construction of molecular assemblies integrated by intermolecular stacking or charge-transfer interactions, clusterization, and ligand-unsupported M-M bonds. The formation of a thin film which acts as an active layer of a field-effect transistor will also be described. Final attention is drawn to the use of the redox-active complexes for the construction of stimuli-responsive molecular assemblies. The review will demonstrate recent developments of molecular assemblies that show macroscopic phase transition or phase transformation triggered by intramolecular electron transfer or redox reaction in solid, liquid, and liquid crystals.

DOI： 10.4019/bjscc.53.24

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その他リンク： https://jlc.jst.go.jp/DN/JALC/00337206410?from=CiNii

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

This paper describes a molecular valence tautomeric (VT) bistability synchronized with polymorphic crystal-melt phase transitions of a newly designed VT complex, [Co(C9Espy)(2)(3,6-DTBQ)(2)] (CoC9Espy, C9Espy = dinonyl-pyridine-3,5-dicarboxylate and 3,6-DTBQ = 3,6-di-tert-butyl-semiquinonate (3,6-DTBSQ) or catecholate (3,6-DTBCat)). Two polymorphic crystals which are the thermodynamically stable phase (K1) and the kinetically stable phase (K2), commonly containing a [low spin-Co(III)(C9Espy)(2)(3,6-DTBSQ)(3,6-DTBCat)] (ls-[Co(III)]) tautomer with a low-spin Co(III) atom and mixed-valence ligands. These polymorphic crystals show a molecular VT interconversion that is synchronized with crystal-to-melt phase transitions at different temperatures, 368.2 and 362.6 K for the ls-[Co(III)]subset of K1 and the ls-[Co(III)]subset of K2 phases, respectively. Interestingly, the ls-[Co(III)]subset of K2 obtained from a melt of a [high spin-Co(II)(C9Espy)(2)(3,6-DTBSQ)(2)] (hs-[Co(II)]) tautomer with a high-spin Co(II) atom with two 3,6-DTBSQ exhibits a double-melting phenomenon that includes, in part, the thermodynamically unfavorable hs-[Co(II)]-to-ls-[Co(III)] VT interconversion. Eventually, three types of VT interconversions synchronized with macroscopic crystal-melt phase transitions appear either in equilibrium or nonequilibrium conditions: (1) the thermodynamically stable ls-[Co(III)]subset of K1 to the hs-[Co(II)]subset of melt, (2) the metastable ls-[Co(III)]subset of K2 to the hs-[Co(II)]subset of melt, and (3) the relaxing process of the metastable hs-[Co(II)]subset of melt to the thermodynamically stable ls-[Co(III)]subset of K1. A new strategy for simultaneous control of molecular states and macroscopic phases using thermodynamically and kinetically formed polymorphic crystalline phases is presented.

DOI： 10.1021/cm900543r

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A zinc complex of biladienone forms a dimer in toluene and dichloromethane. Binding of two molecules of amino alcohols and diamines to the dimer occurs cooperatively, with the first binding constant being two orders OF three orders of magnitude smaller than the second binding constant. Simple amines such as butylamine did not show Such cooperative binding. We suggest the mechanism of cooperative binding, where the amino or hydroxyl group in amino alcohols or diamines prevents the dinner dissociation to result in the less tight binding for the first guest, while the binding of the second ligand caused dimer dissociation to release strain in the intermediate complex. (c) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.11.057

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

A novel alkyl chain-functionalized manganese complex with dioxolene ligands shows a bimodal three-membered valence tautomerism, one of which synchronizes with a cooperative solid-melt phase transition and the other occurs in the melt noncooperatively.

DOI： 10.1039/b901939a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

Dynamic properties of a diruthenium complex with ligand-unsupported Ru-Ru triple bonds, Na(2)[Ru(2)(3,6-DTBCat)(4)] (1), were studied using variable-temperature (1)H NMR. Structural freedom derived from the ligand-unsupported structure leads to torsional motion about the Ru-Ru bonds in THF and in DMF. The observed solvent dependency corresponds to the electrostatic interactions between the diruthenium complex and Na(+) counter cations, which are sensitive to the polarity of solvents. In addition, a new diruthenium complex, [{Na(THF)(2)(H(2)O))[Na(THF)(0.5)(H(2)O)}{Ru(2)(3,6-DTBCat)(2)(H(4)Cat)(2)}] (2-2.5THIF center dot 2H(2)O), with a ligand-unsupported Ru-Ru bond surrounded by two different kinds of catecholate derivatives, has been synthesized and crystallographically characterized. The complex, which was characterized by single-crystal structural analysis, will provide an opportunity to investigate not only static molecular structures but also dynamic physicochemical properties in comparison with analogues containing four identical catecholate derivatives. (c) 2008 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.molstruc.2008.05.027

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Here, we show a synchronic bistability of valence tautomeric (VT) molecular interconversion and a macroscopic crystal-melt phase transition in long alkoxy-functionalized cobalt-dioxolene complexes. Studies have been carried out for a novel series of complexes, [Co(CnOPY)(2)(3,6-DTBQ)(2)] (3,5-dialkoxy(CnH2 On+1-; n = 9, 12, and 17)pyridine (CnOpy) and 3,6-di-tert-butyl semiquinonate or catecholate ligands (3,6-DTBQ)). All complexes show the molecular VT interconversion with thermal hysteresis attributed to the synchronous crystal-melt phase transition. Thermodynamic analysis has revealed that the molecular VT interconversion is restricted over 50 K and crystal-melt phase transition is accelerated about 50 K by the synchronicity. The synchronicity is attributed to enthalpic and entropic effects of the alkoxy chains in the crystalline phase of the one tautomer and the melt phase of the other, respectively. Our results show efficient chemical and thermodynamic strategies to combine molecule-based and macroscopic bistabilities.

DOI： 10.1021/ja711268u

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

We demonstrate a strategy that appears particularly well suited for the design of redox-active liquid crystals and also constitutes the first demonstration of cyclic voltammetric responses of a metallomesogen in the columnar liquid crystalline phase.

DOI： 10.1039/b709103f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic052180p

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Three novel trinuclear cobalt(II) compounds of pyridazine, [CO3(mu-OH)(2)(P-pdz)(4)(pdz)(2)(NO3)(2)(H2O)(2)]-(NO3)(2)(.)(THF)(.)2(MeOH) (1), [Co-3 (mu-OH)(2)(mu-pdz)(4)(pdz)(4) (NO3)(2)] (.) [Co-3 (mu-OH)(2)(P-pdz)(4)(MeOH)(4)(NO3)(2)](.)(NO3)(4) (2), and [Co-3(P-pdz)(4)(mu-NCS)(2)(pdz)(2)(NCS)(4)](.)2MeOH (3) (pdz = pyridazine), have been synthesized and characterized. The structures of all three compounds consist of centrosymmetric trimer building blocks bridged by the two nitrogen atoms of the pyridazine ligands and the second small bridging anions (hydroxide in I and 2, and end-on thiocyanate in 3). The two-atom bridging modes of the pyridazine ligand in 1 and 2 are unusual: each bridging pyridazine ligand affords two nitrogen donors to two metal ions with different bond lengths. This results in two kinds of spin states for the cobalt(II) atoms in 1. Magnetic measurements show a typical antiferromagnetic interaction between the high-spin metals in 3, but an unusual magnetic coupling through two high- and one low-spin cobalt atoms within the trimer in 1. An irregular spin states structure is also observed in 1 at low temperature. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

DOI： 10.1002/ejic.200500741

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

A novel series of valence tautomeric (VT) complexes, [Co(Cnbpy)(3,5-DTBQ)(2)] (Cnbpy = 4,4'-dialkyl-2,2'-bipyridine (alkyl = (CnH2n+1) where n = 0 (CoCObpy), 1 (CoC1bpy), 5 (CoC5bp), 9 (CoC9bpy) and 13 (CoC13bpy); 3,5-DTBQ = 315-di-tert-butylsemiquinonate or catecholate), including two previously reported complexes (CoCObpy and CoC1bpy), were systematically prepared and their properties examined. Introduction of alkyl groups into VT chromophores leads to unexpected variations in the VT process, depending on the lengths of the alkyl chains. An even more interesting observation is that significant polytypic phase transitions with crystallographic symmetry changes accompanying the abrupt VT conversion are induced for the first time in CoC9bpy and CoC13bpy.

DOI： 10.1039/b513807h

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記述言語：日本語   出版者・発行元：THE JAPANESE LIQUID CRYSTAL SOCIETY  

本研究ではレドックス活性配位子を含む遷移金属錯体を基本骨格にカラムナー液晶相を形成する室温液晶の合成及びその性質について報告する。得られたカラムナー液晶はXRDによりヘキサゴナルカラムナーオーダー相に帰属され約２００℃の温度領域で液晶相を発現する。当日はその電気化学応答についても報告する。

DOI： 10.11538/ekitou.2006.0.97.0

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

To explore the relationships between the structures of ligands and their complexes, we have synthesized and characterized a series of metal complexes with two structurally related ligands, 9-acridinecarboxylic acid (HL1) and 4-quinolinecarboxylate acid (HL2), [Cu-2(mu(2)-OMe)2(L-1)2(H2O)(0.69)](n) 1, [Cu-2(L-1)(4)(CH3OH)(2)] 2, [Cu-3(L-1)(6)(CH3OH)(6)]center dot 3H(2)O 3, [Mn-3(L-1)(6)(CH3OH)(6)]center dot 3H(2)O 4, [Co-3(L-1)(6)(CH3OH)(6)]center dot 3H(2)O 5, [Cu(L-2)(2)], 6, [Mn(L-2)(2)(H2O)](n) 7, and [Co(L-2)(2)(H2O)](n) 8. 1 is a three-dimensional (3D) polymer with an interpenetrating NbO type network showing one-dimensional (1 D) channels, whereas 2 and 3 take bi- and trinuclear structures, respectively, because of the differences in basicity of the reaction systems in preparing the three complexes. 4 and 5 have trinuclear structures similar to that of 3. In 1-5, ligand L-1 performs different coordination modes with NO-bridging in 1 and O,O'-bridging in 2-5, and the metal ions also show different coordination geometries: square planar in 1, square pyramidal in 2, and octahedral in 3-5. 6 has a two-dimensional structure containing (4,4) grids in which L-2 adopts the NO-bridging mode and the Cull center takes square planar geometry. 7 and 8 are isostructural complexes showing 1 D chain structures, with L-2 adopting the O,O-bridging mode. In addition, the intermolecular O-H center dot center dot center dot N hydrogen bonds and pi-pi stacking interactions further extend the complexes (except 1 and 6), forming 3D structures. The magnetic properties of 2-7 have been investigated and discussed in detail.

DOI： 10.1021/ic050886d

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ja052663s

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of|rn|Chemistry  

DOI： 10.1039/b506721a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic048250u

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic048251m

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Two novel isomorphous porous frameworks of Ln( III), {[Ln(2)(imidc)(2)(H2O) (3)](H2O)}(n), [Ln = Gd(III) (1) and Er(III) (2)] have been synthesized hydrothermally using multifunctional 4,5-imidazoledicarboxylic acid (imidc) as a connector; they have a zeolite-like network topology which can provide another form upon dehydration, and exhibit selective adsorption properties for H2O over N-2, CO2 and MeOH.

DOI： 10.1039/b500971e

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

DOI： 10.1002/anie.200462962

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Bilindiones and biladienones carrying aryl groups at the meso positions were prepared using coupled oxidation reactions of iron tetraarylporphyrins in 20 - 63% yield.

DOI： 10.1039/b414299c

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/anie.200490079

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Novel metal-complex assemblies constructed from the flexible hinge-like ligand H(2)bhnq (H(2)bhnq= 2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq(2-) ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq(2-) in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq(2-) ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq(2-) ion.

DOI： 10.1002/chem.200305640

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

The magnetic properties of molecular oxygen adsorbed in the micro-porous metal-organic solids have been investigated. Adsorbed O-2 molecules form a ladder structure in the nanochannels of CPL-1. The temperature dependence of susceptibility and the high-field magnetization process indicate the nonmagnetic ground state of the adsorbed O-2 at low temperatures. (C) 2003 Elsevier B. V. All rights reserved.

DOI： 10.1016/j.jmmm.2003.11.327

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

A 2D bilayered ferromagnetic coordination polymer, generated by lower-temperature hydrothermal reactions of cobalt(II) salt with the 3,4-pyridinedicarboxylate dianion, was controlled to transform into a 3D magnetic coordination network with Co-3(OH)(2) ferrimagnetic chains at a higher temperature.

DOI： 10.1039/b312058a

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記述言語：英語   掲載種別：研究論文（国際会議プロシーディングス）   出版者・発行元：SPIE-INT SOC OPTICAL ENGINEERING  

We synthesized novel ligand-based mixed valence (LBMV) Cr-III-dioxolene complexes, [Cr(X(4)SQ)(X(4)Cat)(4,4'-di-tertbutyl-2,2'-bpy)] (SQ = semiquinone, Cat = catecohol, 2,2'-bpy = 2,2'-bipyridine; X = Cl (2a) and Br (2b)) and [Cr(X(4)SQ)(X(4)Cat)(4,4'-dinonyl-2,2'-bpy)] (X = Cl (3a) and Br (3b)), and prepared thin films for investigating their third-order nonlinear optical (NLO) properties in terms of the mixed valence states. Electronic absorption spectra of these complexes in solution and solid states showed an intervalence charge-transfer (IVCT) band from Cat(2-) to SQ(.) at the IR region, indicating of a coexistence of SQ and Cat ligands, namely, LBMV state of the complexes. These complexes were well soluble in nonpolar organic solvent, which allowed us to prepare thin films by spin coating. The obtained films showed the electronic absorption spectra similar to those in solution and were amorphous because of steric hindrance of halogen and alkyl substituents in o-dioxolene and 2,2'-bpy moieties, respectively. The chi((3)) values of the films of 3a and 3b with a thickness of 30 similar to 40 nm were determined for 1.0 x 10(-12) esu at 1.907 mum.

DOI： 10.1117/12.559114

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/anie.200453923

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/anie.200352024

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier  

DOI： 10.1016/S0020-1693(03)00254-8

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

An interesting ferromagnetic linear trinuclear copper(II) compound containing an in-situ synthesised functional ligand has been rationally obtained and crystallographically characterised, confirming a new route to magnetic polynuclear clusters. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

DOI： 10.1002/ejic.200300197

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

A new family of three-dimensional cubic-like [M(dca)(3)](-) networks ( dca = dicyanamide) templated by appropriate cations has been constructed and structurally characterized by X-ray crystallography.

DOI： 10.1039/b300760j

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記述言語：日本語   出版者・発行元：日本液晶学会  

Novel mono/trinuclear palladium/platinum complexes have been synthesized and characterized by X-ray diffraction, electrochemical, and thermogravimetric analyses. All the complexes possess catecholate derivatives, which have been known to show rich redox activity. Almost complexes show multi-step thermal phase transitions, and each transition was studied by XRPD and DSC measurements. Interestingly, the complexes demonstrate redox activity based on the electronically labile nature of the catecholate derivatives. The results obtained in this study clearly suggest that the complexes would be candidates for redox-active metallomesogens.

DOI： 10.11538/ekitou.2003.0_389

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

A novel three-dimensional coordination polymer with a mixed-valence localized copper(I, II) dimeric unit, [Cu-2(4-pya) (3)](n) (4-pya = 4-pyridinecarboxylate), was hydrothermally synthesized via a simultaneous in-situa redox and hydrolysis reaction of Cu(II) and 4-cyanopyridine and crystallographically characterized to be a twofold interpenetrated three-dimensional coordination network with a cubic [Cu-16(4-pya)(12)] building unit.

DOI： 10.1039/b210914j

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER ASSOC ADVANCEMENT SCIENCE  

We report the direct observation of dioxygen molecules physisorbed in the nanochannels of a microporous copper coordination polymer by the MEM (maximum entropy method)/Rietveld method, using in situ high-resolution synchrotron x-ray powder diffraction measurements. The obtained MEM electron density revealed that van der Waals dimers of physisorbed O(2) locate in the middle of nanochannels and form a one-dimensional ladder structure aligned to the host channel structure. The observed O-O stretching Raman band and magnetic susceptibilities are characteristic of the confined O(2) molecules in one-dimensional nanochannels of CPL-1 (coordination polymer 1 with pillared layer structure).

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic0256922

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記述言語：中国語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHINESE CHEMICAL SOCIETY  

The title complex, [Cu(Hsal) (2)(py)(2)], was synthesized by layered-solution technique and structurally characterized by single-crystal X-ray. The copper atom has a square pyramidal geometry and the coordination number is five. The molecular structure is linear one-dimensional network. There is a stacking effect between pyridine ligands of neighbouring 1-D chains and the molecular structure is extended into two-dimensional stacking network. Two salicylates in the complex have a position of crab pincers-like, in which one salicylate is unidentate and another coordinates through the carboxylate group and phenyl group unidentately.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

The treatment of CrIII(X(4)SQ)(3) (SQ = o-semiquinonate; X = Cl and Br) with acetonitrile affords trans-Cr-III(X(4)SQ)- (X(4)Cat)(CH3CN)(2) (X = Cl (1) and Br (2)). In the presence of 2,2'-bipyridine (bpy) or 3,4,7,8-tetramethyl-1,10-phenanthrene (tmphen), the reaction affords Cr-III(X(4)SQ)(X(4)Cat)(bpy)(.)nCH(3)CN (X = Cl, n = 1 (3); X = Br, n = 0.5 (4)) or Cr-III(X(4)SQ)(X(4)Cat)(tmphen) (X = Cl (5) and Br (6)), respectively. All of the complexes show a ligand-based mixed-valence (LBMV) state with SQ and Cat ligands. The LBMV state was confirmed by the presence of the interligand intervalence charge-transfer band. Spectroscopic studies in several solvent media demonstrate that the ligand dissociation included in the conversion of Cr-III(X(4)SQ)(3) to 1-6 occurs only in solvents with relatively high polarity. On the basis of these results, the effects of solvent media were examined and an equilibrium, Cr-III(X(4)SQ)(3) Cr-III(X(4)BQ)(X(4)SQ)(X(4)Cat) (BQ = o-benzoquinone), is proposed by assuming an interligand electron transfer induced by solvent polarity.

DOI： 10.1021/ic025643p

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

Four porous crystalline coordination polymers with two-dimensional frameworks of a double-edged axe-shaped motif, {[Co(NCS)(2)(3-pia)(2)] . 2EtOH . 11 H(2)O}(n) (1a), {[Co(NCS)(2)- (3-pia)(2)] . 4Me(2)CO}(n) (3a), {[Co(NCS)(2)- (3-pia)(2)] . 4THF}(n) (3b) and {[Co(NCS)(2)- (3-pna)(2)](n)} (5), have been synthesized by the reaction of cobalt(ii) thiocyanate with N-(3-pyridyl)isonicotinamide (3-pia) or N-(3-pyridyl)nicotinamide (3-pna). X-ray crystallographic characterization reveals that adjacent layers are stacked such that channels are created, except in 5. The channels form a hydrogen-bonded interior for guest molecules; in practice, I a contains ethanol and water molecules as guests in the channels with hydrogen bonds, whereas 3b (3a) contains tetrahydrofuran (acetone) molecules. In la, the "double-edged axe-shaped" motifs in adjacent sheets are not located over the top of each other, while the motifs in 3b stack so perfectly as to overlap each other in an edge-to-edge fashion. This subtle change in the three-dimensional framework is associated with the template effect of the guests. Compound 5 has no guest molecules and, therefore, the amide groups in one sheet are used for hydrogen-bonding links with adjacent sheets. Removal of the guest molecules from la and 3b (3a) causes a structural conversion accompanied by a color change. Pink 1 a cannot retain its original framework and changes into a blue amorphous compound. On the other hand, the framework of pink 3b (3a) is transformed to a new crystalline framework of violet 4. Interestingly, 4 reverts to the original pink crystals of 3b (3a) when it is exposed to THF (or acetone) vapor. Spectroscopic measurements (visible, EPR, and IR) provide a clue to the crystal-to-crystal transformation; on removal of the guests, the amide groups are used to form the P sheet-type hydrogen bonding between the sheets, and thus the framework withstands significant stress on removal of guest molecules. This mechanism is attributed to the arrangement of the adjacent sheets so suited in regularity that the P sheet-type structure forms efficiently. The apohost 4 does not adsorb cyclopentane, showing a guest selectivity that, in addition to size, hydrogen-bonding capability is required for the guest molecules. The obtained compound is categorized as a member of a new generation of compounds tending towards functional porous coordination polymers.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Reactions of the Rh hydrido complex [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 (1) With nitrogen ligands such as 2-(4-thiazolyl)benzimidazole (tbz). pyridazine (pdz), imidazole (im) and pyrimidine (pmd) in CH,Cl, afforded Various mononuclear Rh hydrido complexes, [Rh(H)(2)(PPh3)(2)(tbz)]CIO4 (2), [Rh(H)(2)(PPh3)(2)(pdZ)(2)]ClO(4)(.)2CH(2)Cl(2) (3). [Rh(H)Cl(PPh3)(2)(pdz)(2)](ClO4CH2Cl2)-C-. (4). [Rh(H)(2)(PPh3)(2)(im)(2)]ClO(4)(.)2CH(2)Cl(2) (5). [Rh(H)Cl(PPh3)(2)(im)(2)](ClO4CH2Cl2)-C-. (6). [Rh(H)(2)(PPh3)(2)(pmd)(2)](ClO4CH2Cl2)-C-. (7) and the Rh non-hydrido complex [RhCl2(pmd)(4)]ClO4 (8). The Rh complexes 2. 3, 5 and 6 were crystallographically characterized. The formation process was monitored by H-1 NMR and UV-Vis spectra. In all the Rh hydrido complexes, the Rh atom is coordinated by two PPh3. ligands in trans-positions and two nitrogen ligands in the cis-positions. The remaining sites Lire occupied by one or two hydride atoms to form a saturated 18-electron framework in a slightly distorted octahedral geometry. For complex 2 an appreciable inter-molecular pi interaction is observed between planes of tbz and PPh3 ligands, while an intra-molecular hydrogen bonding interaction between C-H and Cl atoms is found in complex 6. (C) 2002 Elsevier science Ltd. All rights reserved.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of|rn|Chemistry  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：TAYLOR & FRANCIS LTD  

Three novel one-diniensional coordination polymers with pyridazine (pdz), [M (pdz) Cl-2]n (M = Cu (II) (1), Fe (II) (2), Mn (II) (3)), were synthesized and characterized. All the compounds have one-dimensional zigzag chain structures. The copper ion in compound 1 has a planer coordination sphere with two bridging pdz ligands and two Cl-anions, while the metal ions in the other compounds have a distorted octahedral environment with pdz and Cl- groups both acting as bridges. The magnetic data of these compounds show antiferromagnetic interaction between the magnetic centers within the chains.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Taylor & Francis  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic0010252

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GORDON BREACH SCI PUBL LTD  

The crystal structure of the title complex was first determined, showing a dimeric copper form with the four carboxylate groups. The Cu ... Cu distance is short, associated with the hydrogen bond link of the apically coordinated water molecules with the nearest neighbor vanillic hydroxyl group. The hydrogen bond links afford an infinite 3-D network.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The reaction of tris-tetrahalogeno-o-benzosemiquinonate chromium(III) complexes, [Cr-III(X(4)SQ)(3)] (X=Cl 1a or Br 1b), with bis(cyclopentadienyl) cobalt [(CoCp2)-Cp-II], tetramethyltetraselenafulvalene (TMTSF) and tetrakis(methylsulfanyl)tetrathiafulvalene (TMT-TTF) afforded four charge-transfer compounds, [(CoCp2)-Cp-III][Cr-III(X(4)SQ)(2)(X(4)Cat)] (X=Cl 2a or Br 2b), [TMT-TTF][Cr-III(Br(4)SQ)(2)(Br(4)Cat)] 3b and [TMTSF][Cr-III(Br(4)SQ)(2)(Br(4)Cat)] 4b, where Cat is catecholate. The paramagnetic [Cr-III(X(4)SQ)(2)(X(4)Cat)](-) complexes are commonly formed by cocrystallization with a diamagnetic [(CoCp2)-Cp-III](+) cation for 2a . C6H6 and 2b, and paramagnetic TMT-TTF.+ and TMTSF.+ cations for 3b . C6H5CH3 and 4b . 2CH(2)Cl(2), respectively. The one-electron reduced complexes, [Cr-III(X(4)SQ)(2)(X(4)Cat)](-), with two semiquinonate and one catecholate ligands were isolated and crystallographically characterized. The crystal structures of 2a . C6H6 and 3b . C6H5CH3 consist of alternating stacks of cations and anionic complexes, which form one-dimensional column structures. On the other hand, the anionic complexes in 4b . 2CH(2)Cl(2) form a hexagonal honeycomb network, whose cavities are occupied by the dimerized cation molecules. The temperature dependence of the magnetic susceptibilities reveals that all the [Cr-III(X(4)SQ)(2)(X(4)Cat)](-) complexes are in a ground state of S=1/2, which results from the intramolecular antiferromagnetic interaction between Cr-III(d(3)) and two semiquinonates. In addition, 3b and 4b have a contribution of the paramagnetic TMT-TTF.+ (3b) and TMTSF.+ (4b) cations. In all compounds weak intermolecular magnetic interactions were recognized from the decrease of the chi(m)T values at low temperature.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Taylor & Francis  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Taylor & Francis  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：英語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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記述言語：英語  

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記述言語：日本語   会議種別：口頭発表（一般）  

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