Structural, Magnetic, and Charge-Transport Properties of Stacked Metal Chelate Complexes

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

doi:10.1007/978-1-4684-4175-8_10

Cited by 9 publications

(2 citation statements)

References 184 publications

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“…The oxidation by iodine of phthalocyaninato-like metallomacrocyclic complexes has yielded several number of one-dimensional highly conducting materials. − The most extensively characterized compound in this series is iodine-doped (phthalocyaninato)nickel(II), NiPcI, − the first low-temperature molecular conductor with the conductivity of ca. 600 Ω -1 cm -1 at the ambient temperature .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc₂]I₃·I₂

Janczak

2003

Inorg. Chem.

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Crystals of iodine-doped zirconium(IV) diphthalocyanine, [ZrPc(2)]I(3).I(2) (where Pc = C(32)H(16)N(8)), were grown directly in the reaction of pure zirconium powder with phthalonitrile under a stream of iodine at 260 degrees C. [ZrPc(2)]I(3).I(2) crystallizes in the space group P2(1)/m (No. 11) of the monoclinic system with lattice parameters of a = 6.735(1), b = 25.023(5), and c = 17.440(3) A, beta = 99.43(3) degrees, and Z = 2. The crystals of [ZrPc(2)]I(3).I(2) are built up from two pseudo-monodimensional aggregates: one-electron-oxidized [ZrPc(2)](+) units; weak interacting triiodide I(3)(-) ions with neutral diiodine molecules. The I(3)(-) ions and neutral I(2) molecules in the crystal of [ZrPc(2)]I(3).I(2) have been also detected by Raman spectroscopy. The [ZrPc(2)](+) units form stacks along the a axis, while the polymeric...I(3)(-)...I(2)...I(3)(-)...I(2)(-)... zigzag chains are located in the crystal along the b axis, so both pseudo-monodimensional aggregates are perpendicular to each other. This arrangement is different from that found in the tetragonal crystals of [ZrPc(2)](I(3))(2/3) in which both monodimensional aggregates, i.e., the stacks of partially oxidized [ZrPc(2)](2/3+) units and chains of symmetric triiodide ions, are parallel. EPR experiment together with the X-ray single-crystal analysis clearly shown that oxidation of the diamagnetic ZrPc(2) complex by iodine is ligand centered and homogeneously affecting both phthalocyaninato rings of ZrPc(2); thus, the formal oxidation state of both Pc rings in [ZrPc(2)]I(3).I(2) is nonintegral (-1.5). The UV-vis spectrum of [ZrPc(2)] I(3).I(2) is very similar to the spectrum of unoxidized ZrPc(2) complex in the B Soret and Q spectral region. However, in the spectrum of [ZrPc(2)] I(3).I(2) one additional band at approximately 502 nm is observed, which indicates the existence of the one-electron-oxidized phthalocyaninato(-) radical ligand and is assigned to the electronic transition from a deeper level to the half-occupied HOMO level. The single-crystal electrical conductivity data show anisotropy and nonmetallic character in conductivity (d sigma/dT > 0). The charge transport mainly proceeds along the pseudo-monodimensional stacks of [ZrPc(2)](+) units. The relatively high conductivity along the stacks of one-electron-oxidized [ZrPc(2)](+) units results from the staggering orientation of Pc rings (rotation angle 45.0(2) degrees ) that leads to the short inter-ring C(alpha)(pyrrole)[bond]C(alpha)(pyrrole) contacts (2.839(3)-3.024(3) A). These C(alpha)-pyrrole atoms make appreciable contribution to the partially occupied pi-molecular orbital of Pc macrocycle and the greatest overlap of the HOMO orbitals that form the conduction band of partially oxidized molecular crystals.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc₂]I₃·I₂

Janczak

2003

Inorg. Chem.

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“…45 However, this feature appears commonly for complexes containing partially oxidized, planar platinum cations and anions, and complexes of Pt III . 47 The arrangement of [Pt I (bpy) 2 ](NO 3 )‚2H 2 O appears to be the first example of a one-dimensionally stacked complex of Pt I . The stacking interaction may be important in stabilizing Pt I with a drop in energy of the metal p z orbital that take place with stack formation; 48 π acceptors, such as bipyridine, are expected to lower the energy of the orbital.…”

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Synthesis and Characterization of Bis(2,2‘-bipyridyl)platinum(I): A Novel Microtubular Linear-Chain Complex

et al. 1996

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One-electron reduction of [Pt(bpy)2]2+ (bpy = 2,2‘-bipyridyl) in aqueous solution results in the formation of black-green lustrous needles on solid electrodes. The crystalline needles grow perpendicularly from the substrate surface and reach lengths of 1−2 cm. Elemental analysis, X-ray photoelectron spectroscopy, and electrochemical measurements indicate that the new compound is a genuine PtI complex with a d9 electronic configuration and with the composition [Pt(bpy)2]NO3·2H2O. X-ray crystallographic analysis shows that the crystalline needles consist of linear chains of discrete [PtI(bpy)2] units with a Pt−Pt distance of 3.563(1) Å and with each bipyridyl ligand overlapping face-to-face (eclipsed) with its nearest neighbor. At the monomeric level, the structure of [PtI(bpy)2] units exhibits a distorted square-planar configuration with structural parameters very similar to those of the parent PtII complex, [Pt(bpy)2](NO3)2·H2O. The new linear-chain compound was prepared by chemical and electrochemical methods. The resulting crystals are relatively stable in air but oxidize slowly over a period of weeks. Scanning electron microscopy reveals that the crystals are tubular with a hollow near-hexagonal morphology. Cooperative effects influence the optical and electrical properties of the crystals. Because of extensive solid-state interactions between stacked monomeric [PtI(bpy)2] units, the crystals absorb strongly over the whole visible region and far into the near infrared. Their room temperature electrical conductivity is relatively high, 10 Ω-1 cm-1.

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ChemInform Abstract: Structural, Magnetic, and Charge‐Transport Properties of Stacked Metal Chelate Complexes (213 Literaturzitate).

Hoffman¹,

Martinsen²,

Pace³

et al. 1983

Chemischer Informationsdienst

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Structural, Magnetic, and Charge-Transport Properties of Stacked Metal Chelate Complexes

Cited by 9 publications

References 184 publications

Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc₂]I₃·I₂

Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc₂]I₃·I₂

Synthesis and Characterization of Bis(2,2‘-bipyridyl)platinum(I): A Novel Microtubular Linear-Chain Complex

ChemInform Abstract: Structural, Magnetic, and Charge‐Transport Properties of Stacked Metal Chelate Complexes (213 Literaturzitate).

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Structural, Magnetic, and Charge-Transport Properties of Stacked Metal Chelate Complexes

Cited by 9 publications

References 184 publications

Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc2]I3·I2

Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc2]I3·I2

Synthesis and Characterization of Bis(2,2‘-bipyridyl)platinum(I): A Novel Microtubular Linear-Chain Complex

ChemInform Abstract: Structural, Magnetic, and Charge‐Transport Properties of Stacked Metal Chelate Complexes (213 Literaturzitate).

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Product

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Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc₂]I₃·I₂

Synthesis, Structural Investigation, and Solid-State Properties of Iodine-Doped Zirconium Diphthalocyanine, [ZrPc₂]I₃·I₂