Next Article in Journal / Special Issue
Achievements and Challenges in Molecular Conductors
Previous Article in Journal
Hydrogen Desorption from Mg Hydride: An Ab Initio Study
Previous Article in Special Issue
Chemical Modifications of BDH-TTP [2,5-Bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene]: Control of Electron Correlation
Article Menu

Export Article

Open AccessArticle
Crystals 2012, 2(3), 861-874; doi:10.3390/cryst2030861

Cation Dependence of Crystal Structure and Band Parameters in a Series of Molecular Conductors, β'-(Cation)[Pd(dmit)2]2 (dmit = 1,3-dithiole-2-thione-4,5-dithiolate)

Condensed Molecular Materials Laboratory, RIKEN, 2-1, Hirosawa, Wako-shi, Saitama, 351-0198, Japan
*
Author to whom correspondence should be addressed.
Received: 27 March 2012 / Revised: 25 June 2012 / Accepted: 27 June 2012 / Published: 4 July 2012
(This article belongs to the Special Issue Molecular Conductors)

Abstract

An isostructural series of anion radical salts, β'-(EtxMe4−xZ)[Pd(dmit)2]2 (x = 0–2, Z = P, As, Sb), with a quasi-triangular lattice comprising the dimer unit [Pd(dmit)2]2 belong to a strongly correlated electron system with geometrical frustration. Intra and interdimer transfer integrals between the frontier molecular orbitals, which characterize the strength of electron correlation and degree of frustration, can be tuned by selection of the counter cation. We have systematically analyzed the crystal structure with X-ray diffraction method and intermolecular transfer integrals using extended Hückel molecular orbital calculations based on structural data. The variation in the cation affects the unit cell in a manner equivalent to an anisotropic pressure. Increasing the covalent radius of the central atom Z and the number of ethyl groups (x) in the cation leads to slight arching of the Pd(dmit)2 molecule. This arch-shaped distortion of the Pd(dmit)2 molecule modifies the interdimer transfer integrals in formation of the regular triangular dimer lattice. On the other hand, the intradimer transfer integral, which is correlated with the effective on-site Coulomb interaction of the dimer, is weakly dependent on the type of cation.
Keywords: molecular conductors; strongly correlated electron system; geometrical frustration; X-ray crystal structure analysis; transfer integrals molecular conductors; strongly correlated electron system; geometrical frustration; X-ray crystal structure analysis; transfer integrals
Figures

This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

Supplementary material

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Kato, R.; Hengbo, C. Cation Dependence of Crystal Structure and Band Parameters in a Series of Molecular Conductors, β'-(Cation)[Pd(dmit)2]2 (dmit = 1,3-dithiole-2-thione-4,5-dithiolate). Crystals 2012, 2, 861-874.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Crystals EISSN 2073-4352 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top