Hideki Yamochi

Kyoto University, Kioto, Kyōto, Japan

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Publications (308)877.15 Total impact

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    ABSTRACT: Crystalline anionic coordination complexes (PPN+){CpMo(CO)2(η2-C60)}− (1), (PPN+){CpMo(CO)2- (η2-C70)}−·0.5C6H14 (2) and (PPN+){Cp*Mo(CO)2(η2-C60)}−·C6H5CN·C6H4Cl2 (3) containing cyclopentadienyl (1, 2) and pentamethylcyclopentadienyl (3) molybdenum dicarbonyl η2-coordinated to fullerenes have been obtained by the reaction of the (PPN+)(fullerene•−) salt with the {Cp(*)Mo(CO)3(2)}2 dimers (PPN+ is bis(triphenylphosphoranylidene)ammonium cation). The {CpMo(CO)2(η2-C60(70))}− anions contain neutral C60 and C70. The optical properties and geometry of the CpMo(CO)2 moieties in 1 and 2 are similar to those in (PPN+)-{CpMo(0)(CO)3}−. The analysis of optical data for 3 shows that η2-coordinated C60 molecules are more negatively charged in 3 than in 1 and 2. Complexes 1–3 show weak EPR signals indicating that the major part of the samples is EPR silent and diamagnetic. Diamagnetism of the anions in 1–3 is explained by the chemical bond formation between the initially paramagnetic CpMoI(CO)2 and (fullerene)•− units. The DFT calculations for 1 and 3 support the diamagnetic singlet ground state for both complexes, in which the singlet–triplet energy gaps calculated at the M11/cc-pVTZ-PP/cc-pVDZ level of theory are about 1.27 and 0.95 eV, respectively. According to the calculations, C60 molecules are more negatively charged in 3 than in 1 and that can be explained by stronger back donation from the molybdenum moieties to fullerenes.
    Dalton Transactions 04/2015; 44(20):9672-9681. DOI:10.1039/c5dt00970g · 4.10 Impact Factor
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    ABSTRACT: Coordination of two bridging cobalt atoms to fullerenes by the η(2) type in {Co(dppe)}2{μ2-η(2):η(2)-η(2):η(2)-[(C60)2]}·3C6H4Cl2 [1; dppe = 1,2-bis(diphenylphosphino)ethane] triggers fullerene dimerization with the formation of two intercage C-C bonds of 1.571(4) Å length. Coordination-induced fullerene dimerization opens a path to the design of fullerene structures bonded by both covalent C-C bonds and η(2)-coordination-bridged metal atoms.
    Inorganic Chemistry 04/2015; 54:4597-4599. DOI:10.1021/acs.inorgchem.5b00637 · 4.79 Impact Factor
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    ABSTRACT: Synthetic approaches to iridium complexes of metal phthalocyanines (Pc) and fullerene anions have been developed to give three types of complexes. The compound{(Cp*IrIIII2)SnIIPc(2−)}·2C6H4Cl2 (1) (Cp* is pentamethylcyclopentadienyl) is the first crystalline complex of a metal phthalocyanine in which an iridium(III) atom is bonded to the central tin(II) atom of Pc via a Sn-Ir bond length of 2.58 Å. In (TBA+)(C60•-){(Cp*IrIIII2)SnIIPc(2−)}·0.5C6H14 (2), the {(Cp*IrIIII2)SnIIPc(2−)} units cocrystallize with (TBA+)(C60•-) to form double chains of C60•- anions and closely packed chains of {(Cp*IrIIII2)SnIIPc(2−)}. Interactions between the fullerene and phthalocyanine subsystems are realized through π-π stacking of the Cp* groups of {(Cp*IrIIII2)SnIIPc(2−)} and the C60•- pentagons. Furthermore, the spins of the C60•- are strongly antiferromagnetically coupled in the chains with an exchange interaction J/kB = −31 K. Anionic (TBA+){(Cp*IrIICl)(η2-C60-)}·1.34C6H4Cl2 (3) and (TBA+){(Cp*IrIII)(η2-C60-)}·1.3C6H4Cl2·0.2C6H14 (4) are the first transition metal complexes containing η2-bonded C60- anions, with the Cp*IrIICl and Cp*IrIII units η2-coordinated to the 6-6 bonds of C60-. Magnetic measurements indicate diamagnetism of the {(Cp*IrIICl)(η2-C60-)} and {(Cp*IrIII)(η2-C60-)} anions due to the formation of a coordination bond between two initially paramagnetic Cp*IrIICl or Cp*IrIII groups and C60•- units. DFT calculations support a diamagnetic singlet ground state of 4, in which the singlet-triplet energy gap is greater than 0.8 eV. DFT calculations also indicate that the C60 molecules are negatively charged.
    Organometallics 03/2015; 34(5):879-889. DOI:10.1021/om501210s · 4.25 Impact Factor
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    ABSTRACT: Radical anion salts of metal-containing and metal-free phthalocyanines [MPc(3−)].−, where M=Cu(II), Ni(II), H2, Sn(II), Pb(II), Ti(IV)O, and V(IV)O (1–10) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long CN(imine) bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1–10 show new bands at 833–1041 nm in the NIR range, whereas the Q- and Soret bands are blue-shifted by 0.13–0.25 eV (38-92 nm) and 0.04–0.07 eV (4–13 nm), respectively. Radical anions with Ni(II), Sn(II), Pb(II), and Ti(IV)O have S=1/2 spin state, whereas [Cu(II)Pc(3−)].− and [V(IV)OPc(3−)].− containing paramagnetic Cu(II) and V(IV)O have two S=1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal-free phthalocyanine radical anions [H2Pc(3−)].− (linewidth of 0.08–0.24 mT), broad EPR signals are manifested (linewidth of 2–70 mT) with g-factors and linewidths that are strongly temperature-dependent. Salt 11 containing the [Na(I)Pc(2−)]− anions as well as previously studied [Fe(I)Pc(2−)]− and [Co(I)Pc(2−)]− anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3−)].− in 1–10.
    Chemistry - A European Journal 01/2015; 21:1014-1028. DOI:10.1002/chem.201404925 · 5.70 Impact Factor
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    ABSTRACT: The existence of a spin-disordered quantum state was predicted theoretically by Wannier in 1950 and Anderson in 1973. Various target materials had been considered before the discovery in 2003 of the first quantum spin liquid (QSL) system: a Mott insulator κ-(ET)2Cu2(CN)3, where ET is bis(ethylenedithio)tetrathiafulvalene. The family of dimer-type ET conductors κ-(ET)2X (where X = an anion) exhibits various conduction profiles ranging from insulators to metals to superconductors depending on the counter anion. In κ-(ET)2X, the anion molecules form characteristic patterns of anion openings, on each of which an ET dimer corresponding to a single spin site is positioned, namely a key-keyhole relation. The topological consideration of the crystal structure affords the information on both a spin geometry (t’/t) and electron correlation (U/W), where t and t’ are interdimer transfer interactions with an isosceles triangular geometry, and U and W are the on-site Coulomb repulsion energy and bandwidth, respectively. The QSL system κ-(ET)2Cu2(CN)3 is characterized by a spin lattice containing nearly equilateral triangles (t’/t = 1.09) with strong electron correlations (U/W = 0.93) at room temperature. The temperature dependences of t’/t and U/W are bases to understand the transport and magnetic behaviors of κ-(ET)2X. κ-(ET)2Cu2(CN)3 has a superconducting state next to the QSL state under pressure without passing through an antiferromagnetic state. Here, the design of QSL systems next to a superconducting state is discussed based on the crystal and the electronic structures and physical properties of κ-(ET)2X using the key-keyhole relation and temperature variant band parameters t, t’, U, and W.
    12/2014; 3(6). DOI:10.1039/C4TC01701C
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    ABSTRACT: Radical anion salt (PPN+){Sn(IV)Pc(3-)Cl2}·- (1) was obtained by the reduction of tin(IV) phthalocyanine dichloride {Sn(IV)Pc(2-)Cl2} with (PPN+)(C60·-) (PPN+ is bis(triphenylphosphoranylidene)- ammonium cation). It was shown that the reduction is centered mainly on the Pc ligand providing the appearance of a new band in the spectrum of 1 in the NIR range at 1006 nm and blue-shift of Soret and Q-bands of Sn(IV)Pc(2-)Cl2. The alternation of short and long C–N(imine) bonds for two oppositely located isoindole units in 1 indicates possible disruption of aromaticity of the Pc ligand under reduction. Salt 1 has effective magnetic moment of 1.69 mB at 300 K corresponding to the contribution of one noninteracting S = 1/2 spin per formula unit and manifests antiferromagnetic coupling of spins with Weiss temperature of -7.3 K in the 400–30 K range. The salt shows a broad EPR signal with g = 1.9957 and linewidth of 19.3 mT at room temperature. The signal splits into two components below 120 K. Strong broadening of the EPR signal and shift of g-factors to smaller values in comparison with the EPR signal from radical anions of metal-free phthalocyanine {H2Pc(3-)}·- were attributed to the contribution of the {Sn(III)Pc(2-)Cl2}- admixture with paramagnetic Sn(III). There are p–p stacking one-dimensional chains composed of {Sn(IV)Pc(3-)Cl2}·- in 1 along the a axis with weak overlapping between phenylene groups of phthalocyanine radical anions. The calculated HOMO–HOMO overlap integral is 0.0033 and the SOMO–SOMO overlap integral is only 0.0004. Metallic conductivity is not realized in 1 most probably due to weak SOMO–SOMO overlapping.
    Journal of Porphyrins and Phthalocyanines 12/2014; 18:1157-1163. DOI:10.1142/S1088424614501077 · 1.36 Impact Factor
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    ABSTRACT: Coordination nickel-bridged fullerene polymer [{Ni(Me3P)2}(μ-η(2),η(2)-C60)]∞ (1) has been obtained via reduction of a Ni(II)(Me3P)2Cl2 and C60 mixture. Each nickel atom is linked in the polymer with two fullerene units by η(2)-type Ni-C(C60) bonds of 2.087(8)-2.149(8) Å length. Nickel atoms are coordinated to the 6-6 bonds of C60 as well as two trimethylphosphine ligands to form a four-coordinated environment around the metal centers. Fullerene cages approach very close to each other in the polymer with a 9.693(3) Å interfullerene center-to-center distance, and two short interfullerene C-C contacts of 2.923(7) Å length are formed. Polymer chains are densely packed in a crystal with interfullerene center-to-center distances between fullerenes from neighboring polymer chains of 9.933(3) Å and multiple interfullerene C···C contacts. As a result, three-dimensional dense fullerene packing is formed in 1. According to optical and electron paramagnetic resonance spectra, fullerenes are neutral in 1 and nickel atoms have a zerovalent state with a diamagnetic d(10) electron configuration. The density functional theory calculations prove the diamagnetic state of the polymer with a singlet-triplet gap wider than 1.37 eV.
    Inorganic Chemistry 11/2014; 53:11960-11965. DOI:10.1021/ic501551y · 4.79 Impact Factor
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    ABSTRACT: A compound containing fullerene dimers bonded through two nickel atoms, {Ni(Ph3P)}2(μ2-η(2),η(2)-C60)2·2C6H4Cl2 (), has been obtained as single crystals. The fullerenes are neutral in , showing a zero-valent state of Ni. The nickel atoms are bonded in an η(2) coordination mode with Ni-C distances of 2.001(3)-2.037(3) Å and a close approach of the fullerenes with a 9.716 Å center-to-center distance. The DFT calculations showed a diamagnetic singlet ground state for this dimer.
  • Ken Onda, Hideki Yamochi, Shin-Ya Koshihara
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    ABSTRACT: Conspectus Phenomena that occur in nonequilibrium states created by photoexcitation differ qualitatively from those that occur at thermal equilibrium, and various physical theories developed for thermal equilibrium states can hardly be applied to such phenomena. Recently it has been realized that understanding phenomena in nonequilibrium states in solids is important for photoenergy usage and ultrafast computing. Consequently, much effort has been devoted to revealing such phenomena by developing various ultrafast observation techniques and theories applicable to nonequilibrium states. This Account describes our recent studies of diverse photoinduced dynamics in a strongly correlated organic solid using various ultrafast techniques. Solids in which the electronic behavior is affected by Coulomb interactions between electrons are designated as strongly correlated materials and are known to exhibit unique physical properties even at thermal equilibrium. Among them, many organic charge-transfer (CT) complexes have low dimensionality and flexibility in addition to strong correlations; thus, their physical properties change sensitively in response to changes in pressure or electric field. Photoexcitation is also expected to drastically change their physical properties and would be useful for ultrafast photoswitching devices. However, in nonequilibrium states, the complicated dynamics due to these characteristics prevents us from understanding and using these materials for photonic devices. The CT complex (EDO-TTF)2PF6 (EDO-TTF = 4,5-ethylenedioxytetrathiafulvalene) exhibits unique photoinduced dynamics due to strong electron-electron and electron-phonon interactions. We have performed detailed studies of the dynamics of this complex using transient electronic spectroscopy at the 10 and 100 fs time scales. These studies include transient vibrational spectroscopy, which is sensitive to the charges and structures of constituent molecules, and transient electron diffraction, which provides direct information on the crystal structure. Photoexcitation of the charge-ordered low-temperature phase of (EDO-TTF)2PF6 creates a new photoinduced phase over 40 fs via the Franck-Condon state, in which electrons and vibrations are coherently and strongly coupled. This new photoinduced phase is assigned to an insulator-like state in which the charge order differs from that of the initial state. In the photoinduced phase, translations of component molecules proceed before the rearrangements of intramolecular conformations. Subsequently, the charge order and structure gradually approach those of the high-temperature phase over 100 ps. This unusual two-step photoinduced phase transition presumably originates from steric effects due to the bent EDO-TTF as well as strong electron-lattice interactions.
    Accounts of Chemical Research 10/2014; DOI:10.1021/ar500257b · 24.35 Impact Factor
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    ABSTRACT: The compound containing fullerene dimers bonded through two nickel atoms {Ni(Ph3P)}2(gapta2-eta2,eta2-C60)2∙2C6H4Cl2 (1) has been obtained as single crystals. Fullerenes are neutral in 1 showing zero-valent state of Ni. Nickel atoms are bonded with the gapta2 coordination with Ni-C distances of 2.001(3)-2.037(3) Å and close approach of fullerenes with 9.716 Å center-to-center distance. The DFT calculations showed diamagnetic singlet ground state for this dimer.
    Dalton Transactions 10/2014; 43:17920–17923. · 4.10 Impact Factor
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    ABSTRACT: TTF derivatives decorated with four aryls through the sulfur bridges are employed to form the donor-acceptor type inclusion complexes with fullerenes. The key factor for the formation of inclusion complexes is the introduction of structural flexibility in TTF molecules along with the molecular size matching with fullerene. Crystallographic study indicates that the structures of the resulting complexes are stabilized by multidimensional intermolecular interaction network consisting of TTF cores, peripheral aryls, and fullerenes, which in turn gives rise to the electronic communication between the donor and acceptor as proved by the solid state absorption spectra. Moreover, the fullerene molecules form the two-dimensional sheet structure in the complexes.
    07/2014; 2(38). DOI:10.1039/C4TC01362J
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    ABSTRACT: Two salts containing fullerene C60 and indium(iii) bromide phthalocyanine (Pc) radical anions have been obtained as single crystals: (TBA(+))3(C60˙(-)){In(III)(Br)(Pc)˙(-)}(Br(-))·C6H4Cl2 (1) and (TEA(+))2(C60˙(-)){In(III)(Br)(Pc)˙(-)}·C6H4Cl2·C6H14 (2) where TBA(+) and TEA(+) are tetrabutyl- and tetraethylammonium cations, respectively. The presence of both radical anions is supported by spectra of and in the NIR and IR-ranges. The salts contain zigzag C60˙(-) chains with 10.136 and 10.383 Å center-to-center (ctc) distances in and a uniform ctc distance of 10.186 Å in . In 1, the C60˙(-) radical anions are dimerized in the 180-140 K range to form singly bonded (C60(-))2 dimers, whereas they remain monomeric in 2. Effective packing of planar In(Br)(Pc)˙(-) and spherical C60˙(-) is attained by introducing fullerene spheres between the phenylene substituents of Pc allowing the formation of multiple van der Waals contacts between them. The effective magnetic moment of at 300 K is 2.35μB, indicating a contribution of both C60˙(-) and In(Br)(Pc)˙(-) species having S = 1/2 spin state. There is strong antiferromagnetic coupling of spins between fullerenes in the chains and fullerenes and phthalocyanines in the monomeric phase of 1 with the Weiss temperature of -120 K in the 300-180 K range. The formation of diamagnetic (C60(-))2 dimers switches off magnetic coupling and magnetically isolates In(Br)(Pc)˙(-) (Weiss temperature is only -1 K in the 140-10 K range). Magnetic behavior of 2 is described by the Curie-Weiss law with weak ferromagnetic coupling of spins with Θ = +7.6 K in the 50-300 K range. Both salts manifest single Lorentzian EPR lines at room temperature with g = 1.9911 and a linewidth (ΔH) of 25.4 mT (1) and g = 1.9956 and ΔH = 7.5 mT (2) which can be attributed to both C60˙(-) and In(Br)(Pc)˙(-) species having strong exchange interaction. An asymmetric signal with the main component at g = 1.989-1.965 in the dimeric phase of 1 was attributed to the In(Br)(Pc)˙(-) radical anions.
    Dalton Transactions 07/2014; 43:13061-13069. DOI:10.1039/c4dt01153h · 4.10 Impact Factor
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    ABSTRACT: Fullerene salt {(Ph3P)3Au(+)}2(C60(•-))2(C60)·C6H4Cl2 (1) containing (Ph3P)3Au(+) cations with the C3v symmetry has been obtained as single crystals. Hexagonal corrugated fullerene layers formed in 1 alternate with the layers consisting of (Ph3P)3Au(+) and C6H4Cl2 along the c axis. According to IR spectra and peculiarities of the crystal structure, the charge on fullerenes in the layers is evaluated to be -1 for two and close to zero for one C60. These fullerenes have different cationic surroundings, and positively charged gold atoms approach closer to C60(•-). Charged and neutral fullerenes are closely packed within hexagonal layers with an interfullerene center-to-center distance of 10.02 Å and multiple short van der Waals C···C contacts. The distances between C60(•-) are essentially longer with an interfullerene center-to-center distance of 10.37 Å due to corrugation of the layers, and no van der Waals contacts are formed in this case. As a result, each C60(•-) has only three negatively charged fullerene neighbors with rather long interfullerene distances providing only weak antiferromagnetic interaction of spins in the fullerene layers with a Weiss temperature of -5 K.
    Inorganic Chemistry 06/2014; 53:6850−6855. DOI:10.1021/ic500689n · 4.79 Impact Factor
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    ABSTRACT: (MDABCO+)(C60.−)(TPC) (1), in which MDABCO+ is N-methyldiazabicyclooctanium, TPC is triptycene, and both have threefold symmetry, is a rare example of a fullerene-based quasi-2D metal and contains closely packed hexagonal fullerene layers with interfullerene center-to-center distances of 10.07 Å at 300 K. Evidence for the metallic nature of 1 was obtained by optical and microwave conductivity measurements on single crystals. The metal is characterized by a nontypical Drude response and relatively large optical mass (m*/m0=6.7). The latter indicates a narrow-band nature, which is consistent with the calculated bandwidth of 0.10–0.15 eV. The coexistence of metallic and antiferromagnetic nonmetallic 2D layers was observed in 1 above 200–230 K. It was assumed that the nonmetallic layers undergo a transition to the metallic state below 200 K due to ordering of the fullerene and cationic sublattices. New layered complex (MQ+)(C60.−)(TPC) (2) with a hexagonal arrangement of C60.− was obtained by increasing the interfullerene distance with the bulkier N-methylquinuclidinium cations (MQ+) having threefold symmetry. The structure of 2 is characterized by increased interfullerene center-to-center distances in the layers (10.124, 10.155, and 10.177 Å at 250 K). Unit-cell doubling parallel to the 2D layer (along the b axis) was observed at low temperatures. In contrast to metallic 1, 2 exhibits a nonmetallic spin-frustrated state with an antiferromagnetic interaction of spins (the Weiss temperature is −27 K) and no magnetic ordering down to 1.9 K. It was supposed that the expanded interfullerene distances in the triangular arrangement decrease the bandwidth and suppress metallic conductivity in 2, and thus a Mott–Hubbard insulating state with antiferromagnetically frustrated spins results.
    Chemistry - A European Journal 06/2014; 20:7268–7277. DOI:10.1002/chem.201304763 · 5.70 Impact Factor
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    ABSTRACT: A new salt, (MDABCO+)(C60.−) (1; MDABCO+=N-methyldiazabicyclooctanium cation), was obtained as single crystals. The crystal structure of 1 determined at 250 and 100 K showed 3D close packing of fullerenes with eight fullerene neighbors for each C60.−. These neighbors are located at 10.01–10.11 Å center-to-center distances (250 K) and van der Waals interfullerene C⋅⋅⋅C contacts are formed with four fullerene neighbors arranged in the bc plane. Fullerene ordering observed below 160 K is accompanied by the appearance of one and a half independent C60.− and trebling of the unit cell along the b axis. Fullerenes are packed closer to each other at 100 K. As a result, fullerenes are located in the three-dimensional packing at 9.91–10.12 Å center-to-center distances and 18 short interfullerene C⋅⋅⋅C contacts are formed for each C60.−. Although they are closed packed, fullerenes are not dimerized down to 1.9 K. Magnetic data indicate strong antiferromagnetic coupling of spins in the 70–300 K range with a Weiss temperature of Θ=−118 K. Magnetic susceptibility shows a round maximum at 46 K. Such behavior can be described well by the Heisenberg model for square two-dimensional antiferromagnetic coupling of spins with an exchange interaction of J/kB=−25.3 K. This magnetic coupling is one of the strongest observed for C60.− salts.
    Chemistry - An Asian Journal 06/2014; 9:1629-1635. DOI:10.1002/asia.201402048 · 3.94 Impact Factor
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    ABSTRACT: Iron hexadecachlorophthalocyanine (Cl16Pc) salts with a layered arrangement of phthalocyanine (Pc) macrocycles were obtained by the reduction of FeCl16Pc with sodium fluorenone ketyl in the presence of PPNCl [PPN+: bis(triphenylphosphine)iminium cation] and TBABr (TBA+: tetrabutylammonium cation). (PPN+)[{Fe(I)Cl16Pc}–]·0.78C6H4Cl2·0.22C6H14 (1) contains π–π stacking columns formed by dimerized {Fe(I)Cl16Pc}– anions. The side-by-side arrangement of neighboring columns results in the formation of a layered iron hexadecachlorophthalocyanine structure. (TBA+)3{[(FeCl16Pc)2]3–} (2) contains hexagonal layers formed by [(FeCl16Pc)2]3– dimers and separated by TBA+ cations. The dimers bear –3 charge and, according to optical and X-ray diffraction data, consist of a [Fe(I)(Cl16Pc)]– monoanion and a [Fe(0)(Cl16Pc)]2– dianion. These anions are bonded in the dimer by a Fe–Fe bond of 2.899(4) Å length. It was shown that the negative charge in both anions is localized on the iron atoms to form Fe(I) and Fe(0), respectively, and no electron transfer to the hexadecachlorophthalocyanine macrocycles is observed. Magnetic data indicate the presence of only one S = 1/2 spin per [(FeCl16Pc)2]3– dimer. This result is in agreement with the formation of iron(I) and iron(0) hexadecachlorophthalocyanine anions, which have the iron atoms in d7 and diamagnetic d8 electron configuration, respectively. The spins of the iron(I) atoms are arranged in a hexagonal manner and only weakly interact, which results in a Weiss temperature of –1 K because of the long distances between them (>18 Å). Previously studied anionic salts with a columnar arrangement of [Fe(I)(Cl16Pc)]– do not show EPR signals from FeI. In contrast, salt 2 shows an intense EPR signal with main components at g(per) = 2.249 and g∥ = 1.989, which are characteristic of Fe(I) with d7 electron configuration.
    Berichte der deutschen chemischen Gesellschaft 05/2014; DOI:10.1002/ejic.201400126
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    ABSTRACT: Compounds of the formula (EDO-TTF-Cl)2XF6 (EDO-TTF-Cl = 4-chloro-4′,5′-ethylenedioxytetrathiafulvalene, X = As, Sb) were prepared to examine the substituent size effect on the packing structure of the donor molecules. In these salts, a head-to-tail type donor stacking was observed. Although the AsF6 salt is a quasi-one-dimensional dimer Mott insulator, the SbF6 salt shows quasi-one-dimensional metallic behavior. Detailed crystal structure analyses revealed the correlation between the anion size and the intermolecular slipping among the donor molecules. The donor morphology, which plays an important role in the overlapping mode selectivity, is characterized by the magnitude and configuration of the out-of-plane substituent size.
    Berichte der deutschen chemischen Gesellschaft 04/2014; 2014(24). DOI:10.1002/ejic.201400128

Publication Stats

4k Citations
877.15 Total Impact Points

Institutions

  • 1991–2015
    • Kyoto University
      • Division of Chemistry
      Kioto, Kyōto, Japan
    • University of California, Santa Barbara
      • Department of Chemistry and Biochemistry
      Santa Barbara, California, United States
    • Okayama University
      • Department of Chemistry
      Okayama, Okayama, Japan
  • 1985–2010
    • Osaka University
      • • Department of Macromolecular Science
      • • Department of Chemistry
      • • Institute for Protein Research
      Suika, Ōsaka, Japan
  • 2007
    • Fukui University of Technology
      Hukui, Fukui, Japan
  • 2005
    • Tokyo Institute of Technology
      • Department of Materials Science and Engineering
      Edo, Tōkyō, Japan
  • 1997–2003
    • The Graduate University for Advanced Studies
      Миура, Kanagawa, Japan
  • 2001
    • Lodz University of Technology
      Łódź, Łódź Voivodeship, Poland
  • 1986–1995
    • The University of Tokyo
      • Institute for Solid State Physics
      Tōkyō, Japan
    • Kobe University
      • Department of Chemistry
      Kōbe, Hyōgo, Japan
  • 1990
    • Okayama University of Science
      • Faculty of Science
      Okayama, Okayama, Japan
  • 1985–1988
    • Nagoya University
      • Department of Chemistry
      Nagoya-shi, Aichi-ken, Japan