Conductive molecular crystals. Structural, magnetic, and charge-transport properties of partially oxidized (5,10,15,20-tetramethylporphyrinato)nickel(II)

Pace, Laurel J.; Martinsen, Jens; Ulman, Abraham; Hoffman, Brian M.; Ibers, James A.

doi:10.1021/ja00347a016

Cited by 54 publications

(36 citation statements)

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“…There is an $4 ruffling of the core, with angles between adjacent pyrrole rings ranging from 21.7 to 28.6 °. These angles are not unusual for S4-ruffled nickel porphyrins, as Ni(oep) has an angle of about 23 ° between adjacent rings (Meyer, 1972), while Ni(tmp)I has a value of 17.5 ° for this angle (Pace, Martinsen, Ulman, Hoffman & Ibers, 1982). It has been suggested that overall puckering, such as that observed here, may result from optimization of Ni-N bonding upon disruption of the zr system , with the Ni-N bond distances decreasing in order to approach the normal 1.85 A bond length for a square-planar monodentate system (Sacconi, 1968).…”

Section: Description Of the Structuresmentioning

confidence: 95%

The structures of (5,10,15,20-tetramethylporphyrinato)nickel(II) and (5,10,15,20-tetramethylchlorinato)nickel(II)

Gallucci¹,

Swepston²,

Ibers³

1982

Acta Crystallogr Sect B

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Section: Description Of the Structuresmentioning

confidence: 95%

The structures of (5,10,15,20-tetramethylporphyrinato)nickel(II) and (5,10,15,20-tetramethylchlorinato)nickel(II)

Gallucci¹,

Swepston²,

Ibers³

1982

Acta Crystallogr Sect B

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“…It is convenient to define occupation numbers rij = c\Cj in the case of a canonical one-particle basis diagonalizing the HF (CO) operator; the rij set fulfills the idempotency relation (11).…”

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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“…They are included in DNA, RNA, in content of vitamins of B group, antibiotics, vessel expanding medicines, correcting heart action, stimulating metabolic processes. [3][4][5][6][7][8] Some of CT complexes were used as current controlled electrically, switched memory, 9 conducting single crystals in the microcircuitry of electronic devices, 10 components of solar cells 11 and semiconductors 12 making use of their high-electrical conductivity. 13,14 Recently, a lot of interest in molecular CT complexes has stemmed from their technological potential.…”

Section: Introductionmentioning

confidence: 99%

Charge Transfer Complexes of Some Heterocyclic Aromatic Amines with π‐Organic Acceptors in Polar Solvents

Abdalla

El-Haty

Adam

et al. 2013

J Chinese Chemical Soc

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A conductometric titration technique has been used to investigate the electron transfer activity of CT molecular complexes formed by arylazopyrimidine and naphthylazopyrimidine derivatives as donors and the organic p-acceptors p-nitroaniline, p-chloroaniline, p-bromoaniline, anthraquinone, picric acid, anitroso-b-naphthol, p-hydroxybenzaldehyde and maleic anhydride. The study was performed at different degree of temperature and in three different polar solvents namely N,N-dimethylformamide (DMF), acetonitrile (ACN) and dimethylsulfoxide (DMSO). The stoichiometric ratios of these complexes were found to be 1:1. The dissociation constant (as M ) values of the formed complexes have been calculated, and the effects of solvents as well as types of electron donors on their conductance s p -values have been examined.

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Conductive molecular crystals. Structural, magnetic, and charge-transport properties of partially oxidized (5,10,15,20-tetramethylporphyrinato)nickel(II)

Cited by 54 publications

References 1 publication

The structures of (5,10,15,20-tetramethylporphyrinato)nickel(II) and (5,10,15,20-tetramethylchlorinato)nickel(II)

The structures of (5,10,15,20-tetramethylporphyrinato)nickel(II) and (5,10,15,20-tetramethylchlorinato)nickel(II)

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

Charge Transfer Complexes of Some Heterocyclic Aromatic Amines with π‐Organic Acceptors in Polar Solvents

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