The (phthalocyaninato)copper iodide complex Cu(pc)I: a molecular metal with a one-dimensional array of local moments embedded in a "Fermi sea" of charge carriers

Ogawa, Michael Y.; Martinsen, Jens; Palmer, Sharon M.; Stanton, J. L.; Tanaka, Jirō; Greene, R. L.; Hoffman, Brian M.; Ibers, James A.

doi:10.1021/ja00238a021

Cited by 154 publications

(65 citation statements)

References 2 publications

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“…3b) with alternatively aligned charged MPc þ and neutral MPc layers were adopted in calculations of transfer integrals as a function of interplanar distance, CoPc, 71 NiPc, 72 CuPc, 73 and H 2 Pc. , when the external part of reorganization energy is also taken into consideration.…”

Section: Discussionmentioning

confidence: 99%

Charge transport in stacking metal and metal‐free phthalocyanine iodides. Effects of packing, dopants, external electric field, central metals, core modification, and substitutions

Chen

2009

J Comput Chem

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The charge-transport properties of the one-dimensional stacking metal phthalocyanine iodides (M(Pc)I, M = Fe, Co, Ni, Cu) and metal-free phthalocyanine iodide (H2(Pc)I) have been theoretically investigated. On the basis of the tight-binding approximation and two-state theory, both the site-energy corrected energy splitting in dimer and Fock-matrix-based methods are used to calculate the transfer integral. The intermolecular motions, including interplanar translation, rotation, slip, and tilt, exert remarkable impacts on the transfer integral. The order/disorder of the dopant stack and the long-range electrostatic interactions are also demonstrated to be crucial factors for modulation of charge-transport properties. The transfer integral undergoes slight changes under an applied electric field along the stacking direction in the range of 10(6)-10(7) V cm(-1). The change of central metals in MPc has little effect on the transfer integrals, but significantly affects the reorganization energies. The extension of the pi-conjugation in macrocyclic ligand brings about considerable influence on the transfer integrals. Peripheral substitutions by animo, hydroxyl, and methyl lead to deviations from planarity of macromolecular rings, and hence affect the valence bands significantly.

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Section: Discussionmentioning

confidence: 99%

Charge transport in stacking metal and metal‐free phthalocyanine iodides. Effects of packing, dopants, external electric field, central metals, core modification, and substitutions

Chen

2009

J Comput Chem

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“…This has already been accomplished in 1986 with the preparation of the metallic conductor (s RT 1 2 ) on the Cu 2+ ion situated within the partially oxidized Pc ring that contains the mobile conduction electrons (2,3). An interaction between the localized and mobile spins has been reported.…”

Section: Introductionmentioning

confidence: 99%

A New Paramagnetic Pd(dmit)2 Salt: Tris(2,2′-Bipyridine)Nickel(II) Bis(1,3-Dithiole-2-Thione-4,5-Dithiolato)Palladate(II) Mono-Acetonitrile; [Ni(bpy)3][Pd(dmit)2]·CH3CN

Mulder

Faulmann

Haasnoot

et al. 2002

Journal of Solid State Chemistry

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“…The metal-phthalocyanine molecule is advantageous, since it provides the -d interaction between the electron conduction of the phthalocyanine molecular orbitals and the local moment of the central transition metal. [5][6][7][8] Figure 1(a) shows the dicyano(phthalocyaninato)iron [Fe(Pc)(CN) 2 ] molecule. 9) In this letter, we report the magnetoresistance and its dependence on the magnetic field angle in the Fe(Pc)(CN) 2 molecular complexes.…”

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confidence: 99%

Giant Negative Magnetoresistance Reflecting Molecular Symmetry in Dicyano(phthalocyaninato)iron Compounds

et al. 2006

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Materials containing Fe(Pc)(CN) 2 dicyano(phthalocyaninato)iron molecules show a giant negative magnetoresistance from the interaction between the conduction and the local moment. Under a magnetic field, the resistance becomes two orders of magnitude smaller than the zero-field resistance. The magnetic-field-angle dependence of the magnetoresistance reflects the symmetry of the Fe(Pc)(CN) 2 molecule. We discuss, according to the scaling relation, the correlation between the magnetoresistance and the molecular spin fluctuation. The giant response of spin-dependent transport has made many important contributions to physics and has been applied to magnetic storage and sensors, such as gigantic magnetoresistance.1) For molecular application, giant magnetoresistance in molecular materials is a key phenomenon. The intermolecular or intramolecular interaction between the conduction and the local moments is indispensable. Several studies have focused on molecular conductors having an interaction (-d interaction) between the molecules contributing to the conduction of the electron and the other molecules contributing to the magnetism of the d electron.2,3) In these conductors, it is important to control the molecular arrangement in the crystal. 4) If a single molecule contributes to both the electron conduction and the local moments, one can expect the possibility of an intramolecular -d interaction independent of the molecular arrangement. The physical properties resulting from the intramoleculard interaction can be realized not only in the crystal but in other various forms, such as film. The metal-phthalocyanine molecule is advantageous, since it provides the -d interaction between the electron conduction of the phthalocyanine molecular orbitals and the local moment of the central transition metal. 9) In this letter, we report the magnetoresistance and its dependence on the magnetic field angle in the Fe(Pc)(CN) 2 molecular complexes. The various Fe(Pc)(CN) 2 complexes show a giant negative magnetoresistance reflecting the molecular symmetry. The -d interaction causes a giant negative magnetoresistance in various compounds, in spite of the different molecular arrangements. Because the CN ligands of the Fe(Pc)(CN) 2 molecule markedly improve its solubility, the CN-ligands enable not only the growth of the molecular crystal but also the fabrication of a molecular thin film by a wet process. The needlelike single crystal is synthesized by the electrochemical method.9,11) The proportions of iron and cobalt atoms in the alloy TPP[Fe x Co 1Àx (Pc)(CN) 2 ] 2 are investigated by electron probe micro analysis (EPMA). Gold wires were glued with gold paint to the sample surface, and dc resistance was measured. A constant current (or voltage) was applied along the c axis, and sample voltage (or current) was measured. The experiments were performed with an 18 T superconducting magnet and a pulse magnet.

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The (phthalocyaninato)copper iodide complex Cu(pc)I: a molecular metal with a one-dimensional array of local moments embedded in a "Fermi sea" of charge carriers

Cited by 154 publications

References 2 publications

Charge transport in stacking metal and metal‐free phthalocyanine iodides. Effects of packing, dopants, external electric field, central metals, core modification, and substitutions

Charge transport in stacking metal and metal‐free phthalocyanine iodides. Effects of packing, dopants, external electric field, central metals, core modification, and substitutions

A New Paramagnetic Pd(dmit)2 Salt: Tris(2,2′-Bipyridine)Nickel(II) Bis(1,3-Dithiole-2-Thione-4,5-Dithiolato)Palladate(II) Mono-Acetonitrile; [Ni(bpy)3][Pd(dmit)2]·CH3CN

Giant Negative Magnetoresistance Reflecting Molecular Symmetry in Dicyano(phthalocyaninato)iron Compounds

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