(Tetrabenzoporphyrinato)nickel(II) iodide. A doubly mixed valence molecular conductor

Martinsen, Jens; Pace, Laurel J.; Phillips, Terry E.; Hoffman, Brian M.; Ibers, James A.

doi:10.1021/ja00365a018

Cited by 108 publications

(55 citation statements)

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“…Vibrational bands of TTF were assigned to the absorptions at 827 cm " 1 (p16), 1280 cm°1 (u 23 comparison with reported spectra [25]. The u 16 and at 270, 364, and 486 ni for (TTF) 4 CuBr 2 . The low energy absorption band above 500 nm which is often found in conducting TTF compounds [26] was part of the broad background and a specific wavelength could not be assigned.…”

Section: Resultsmentioning

confidence: 82%

Synthesis and characterization of tetrathiafulvalene charge transfer compounds with copper halides

Kim

Hatfield

1991

Inorganica Chimica Acta

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Section: Resultsmentioning

confidence: 82%

Synthesis and characterization of tetrathiafulvalene charge transfer compounds with copper halides

Kim

Hatfield

1991

Inorganica Chimica Acta

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“…The Zn 2 + was removed [12] with H 2 SO 4 , and the metals were incorporated into H 2 -TBP using dimethylformamide (DMF) for Cd(II), Cu(II) [22], pyridine for Ni(II) [18], benzonitrile for VO(IV), and magnesium hexapyridine diiodide for Mg(II) [15]. These complexes were purified on thin layer silica gel plates using methanol/chloroform/pyridine mixtures as the elutants.…”

Section: Experimental*mentioning

confidence: 99%

“…A one-pot template method now yields gram quantities of Zn-TBP [7], and both ring [8] and meso-substituted species [9,10] have been prepared. Recent work has appeared on Fe [11], Pt [12,13], Pd [12], Zn [6,14], Cd [15], Mg [15], Co [16] and Ge [16] complexes, and ring-oxidized M-TBP iodides [17,18], where M stands for a metal. The spectrum of Mg-TBP resembles that of chlorophyll [19] and it has been suggested [20] that both H 2 -TBP and Mg-TBP(py) 2 , where py stands for pyridine (as well as the chlorin of porphin [21]) are constituents of interstellar dust.…”

Section: Introductionmentioning

confidence: 99%

Tetrabenzoporphyrins: Metal Incorporation and Exchange Kinetics, Ligational Equilibria and Pulse Radiolysis Studies

Cromer

Hambright

Grodkowski

et al. 1997

J. Porphyrins Phthalocyanines

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The solution chemistry of tetrabenzoporphyrin ( TBP ) and several of its metal derivatives were compared with that of the corresponding octaethylporphyrins. Kinetic studies were done on zinc and cadmium ion incorporation and the exchange reactions of cadmium porphyrins with zinc. Formation constants of Cd (II), Cu (II), VO (IV), Ni (II), Zn (II) and Mg (II) porphyrins with pyridine were determined for both compounds. The spectra of the radical cations of Ni (II), Mg (II) and H 2- TBP were obtained, as well as that of the radical anion of Mg (II)- TBP . Aside from the new Ni (I)- TBP , no long-lived intermediates, as noted with other porphyrins, were observed upon reduction of the tetrabenzoporphyrins. The low basicity and rigidity of the tetrabenzoporphyrin nucleus may explain many of its relative reactivity properties.

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“…To derive the GC HF operator in the CO scheme field operators i// (/•) and (/•) are defined in terms of an orthogonal basis /, (/•) and annihilationcreation operators c, and cf, that obey the conve nient anticommutation rules of (10). …”

Section: The Grand Canonical (Gc) Averaging-procedures In the Crystal mentioning

confidence: 99%

“…On one side, it is possible that the conducting states dispose of significant admixtures from the metal and ligand subspaces; on the other, one has to take into account degeneracies or neardegeneracies between both types of conducting states (doubly mixed valence solids). The rich vari ety of possible transfer mechanisms in metallomacrocycles has been demonstrated in a series of Ni(II) porphyrinato materials [9][10][11]. Polaronic transport properties have been detected in ID chains with large lattice spacings c(c> 3.75Ä ), c numbers < 3.25 A lead to band conductivities.…”

Section: Introductionmentioning

confidence: 99%

Symmetry Violations in Partially Oxidized One-Dimensional (1D)Transition Metal Polymers. Metal-Ligand-Metal(M-L-M) Bridged Systems

Böhm

1984

Zeitschrift Für Naturforschung A

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The band structure of the metal-ligand-metal (M-L-M) bridged quasi one-dimensional (ID) cyclopentadienylmanganese polymer, MnCp 1, has been studied in the unoxidized state and in a partly oxidized modification with one electron removed from each second MnCp fragment. The tight-binding approach is based on a semiempirical self-consistent-field (SCF) Hartree-Fock (HF) crystal orbital (CO) model of the INDO-type (intermediate neglect of differential overlap) combined with a statistical averaging procedure which has its origin in the grand canonical ensemble. The latter approximation allows for an efficient investigation of violations of the trans lation symmetries in the oxidized ID material. The oxidation process in 1 is both ligand-and metal-centered (Mn 3d.2 states). The mean-field minimum corresponds to a charge density wave (CDW) solution with inequivalent Mn sites within the employed repeat-units. The symmetry adapted solution with electronically identical 3d centers is a maximum in the variational space. The coupling of this electronic instability to geometrical deformations is also analyzed. The ligand amplitudes encountered in the hole-state wave function prevent extremely large charge separations between the 3d centers which are found in ID systems without bridging moieties (e.g. Ni(CN)g~ chain). The symmetry reduction in oxidized 1 is compared with violations of spatial symmetries in finite transition metal derivatives and simple solids. The stabilization of the valence bond-type (VB) solution is physically rationalized (i.e. left-right correlations between the 3d centers). The computational results derived for 1 are generalized to oxidized transition metal chains with band occupancies that are simple fractions of the number of stacking units and to ID systems that deviate from this relation. The entropy-influence for temperatures 7* + 0 is shortly discussed (stabilization of domain or cluster structures). S y m m e try V io la tio n s in P a r t i a l l y O x id iz e d O n e -D im e n s io n a l ( I D ) T r a n s itio n M e ta l P o ly m e r s . M e ta l-L ig a n d -M e ta l ( M -L -M ) B rid g e d S y s te m s IntroductionThe structural, optical, magnetic, chemical and charge carrier properties of low-dimensional mate rials with organometallic building blocks have been studied extensively in the past decade [1 -5]. A large number of systems show semiconducting or highly conducting properties in solids that crystal lize in form of segregated stacks (i.e. adjacent donor and acceptor strands). This arrangement often leads to an incomplete charge transfer between the two one-dimensional columns. Different types of stack ing patterns are accessible in such systems with 3d, 4d or 5d atoms as central units and a broad spec trum of organic ligands. The transfer channels and the transport mecha nisms of these materials can be modified by changes in the molecular skeletons or counterions. It is pos sible to discriminate two different carrier paths even in the simplest, highly idealized description: a) ID stacks ...

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(Tetrabenzoporphyrinato)nickel(II) iodide. A doubly mixed valence molecular conductor

Cited by 108 publications

References 0 publications

Synthesis and characterization of tetrathiafulvalene charge transfer compounds with copper halides

Synthesis and characterization of tetrathiafulvalene charge transfer compounds with copper halides

Tetrabenzoporphyrins: Metal Incorporation and Exchange Kinetics, Ligational Equilibria and Pulse Radiolysis Studies

Symmetry Violations in Partially Oxidized One-Dimensional (1D)Transition Metal Polymers. Metal-Ligand-Metal(M-L-M) Bridged Systems

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