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Title: Spin pairing and magnetic coupling in quasi one-dimensional semiconductors with a trimeric stacking structure. Structural, charge-transport, and magnetic studies of (Ni(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl and (Cu(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl

Abstract

Electrochemical oxidation of (triazatetrabenzoporphyrinato)nickel(II) or (triazatetrabenzoporphyrinato)copper(II), Ni(tatbp) or Cu(tatbp), dissolved in 1-chloronaphthalene in the presence of the perrhenate ion affords the new molecular conductors (Ni(tatbp)){sub 3}(ReO{sub 4}){sub 2}{center dot}C{sub 10}H{sub 7}Cl and (Cu(tatbp)){sub 3}(ReO{sub 4}){sub 2}{center dot}C{sup 10}H{sub 7}Cl. The isostructural compounds are composed of partially ligand-oxidized (+2/3) M(tatbp) molecules that form trimerized stacks. Trimerization of the conducting stacks renders the compounds semiconductors with conductivity along the needle axis (crystallographic a) in the range of 2.5 {times} 10{sup {minus}4}-3.0 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1} and an activation energy for conduction in the range of 0.24-0.26 eV. Magnetic susceptibility measurements on the Ni(II) derivative show that the valence band has the diamagnetic ground state expected for a semiconductor. Nonetheless, the valence-band electrons are shown to mediate a strong intratrimer Cu-Cu coupling characterized by a Weiss constant {Theta} = {minus}5.2 K in the Cu(II) analogue. The magnetic properties are rationalized in terms of a band structure derived by considering the trimers as weakly interacting supermolecules, with {Theta} dominated by intratrimer interactions. A structure determination was performed on the Cu(II) analogue.

Authors:
; ; ;  [1]
  1. Northwestern Univ., Evanston, IL (USA)
Publication Date:
OSTI Identifier:
5469914
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (United States)
Additional Journal Information:
Journal Volume: 112:20; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; SEMICONDUCTOR MATERIALS; CHARGE TRANSPORT; CRYSTAL STRUCTURE; MAGNETIC PROPERTIES; COPPER COMPLEXES; MAGNETIC SUSCEPTIBILITY; NICKEL COMPLEXES; RHENIUM COMPLEXES; TRICLINIC LATTICES; COMPLEXES; CRYSTAL LATTICES; MATERIALS; PHYSICAL PROPERTIES; TRANSITION ELEMENT COMPLEXES; 360602* - Other Materials- Structure & Phase Studies; 360603 - Materials- Properties

Citation Formats

Godfrey, M R, Newcomb, T P, Hoffman, B M, and Ibers, J A. Spin pairing and magnetic coupling in quasi one-dimensional semiconductors with a trimeric stacking structure. Structural, charge-transport, and magnetic studies of (Ni(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl and (Cu(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl. United States: N. p., 1990. Web. doi:10.1021/ja00176a028.
Godfrey, M R, Newcomb, T P, Hoffman, B M, & Ibers, J A. Spin pairing and magnetic coupling in quasi one-dimensional semiconductors with a trimeric stacking structure. Structural, charge-transport, and magnetic studies of (Ni(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl and (Cu(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl. United States. doi:10.1021/ja00176a028.
Godfrey, M R, Newcomb, T P, Hoffman, B M, and Ibers, J A. Wed . "Spin pairing and magnetic coupling in quasi one-dimensional semiconductors with a trimeric stacking structure. Structural, charge-transport, and magnetic studies of (Ni(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl and (Cu(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl". United States. doi:10.1021/ja00176a028.
@article{osti_5469914,
title = {Spin pairing and magnetic coupling in quasi one-dimensional semiconductors with a trimeric stacking structure. Structural, charge-transport, and magnetic studies of (Ni(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl and (Cu(tatbp)) sub 3 (ReO sub 4 ) sub 2 ter dot C sub 10 H sub 7 Cl},
author = {Godfrey, M R and Newcomb, T P and Hoffman, B M and Ibers, J A},
abstractNote = {Electrochemical oxidation of (triazatetrabenzoporphyrinato)nickel(II) or (triazatetrabenzoporphyrinato)copper(II), Ni(tatbp) or Cu(tatbp), dissolved in 1-chloronaphthalene in the presence of the perrhenate ion affords the new molecular conductors (Ni(tatbp)){sub 3}(ReO{sub 4}){sub 2}{center dot}C{sub 10}H{sub 7}Cl and (Cu(tatbp)){sub 3}(ReO{sub 4}){sub 2}{center dot}C{sup 10}H{sub 7}Cl. The isostructural compounds are composed of partially ligand-oxidized (+2/3) M(tatbp) molecules that form trimerized stacks. Trimerization of the conducting stacks renders the compounds semiconductors with conductivity along the needle axis (crystallographic a) in the range of 2.5 {times} 10{sup {minus}4}-3.0 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1} and an activation energy for conduction in the range of 0.24-0.26 eV. Magnetic susceptibility measurements on the Ni(II) derivative show that the valence band has the diamagnetic ground state expected for a semiconductor. Nonetheless, the valence-band electrons are shown to mediate a strong intratrimer Cu-Cu coupling characterized by a Weiss constant {Theta} = {minus}5.2 K in the Cu(II) analogue. The magnetic properties are rationalized in terms of a band structure derived by considering the trimers as weakly interacting supermolecules, with {Theta} dominated by intratrimer interactions. A structure determination was performed on the Cu(II) analogue.},
doi = {10.1021/ja00176a028},
journal = {Journal of the American Chemical Society; (United States)},
issn = {0002-7863},
number = ,
volume = 112:20,
place = {United States},
year = {1990},
month = {9}
}