NEW FUNCTIONALIZED TETRATHIAFULVALENES - X-RAY CRYSTAL-STRUCTURES AND PHYSICOCHEMICAL PROPERTIES OF TTF-C(O)NME(2) AND TTF-C(O)-O-C4H9 - A JOINT EXPERIMENTAL AND THEORETICAL-STUDY

被引:63
作者
BATSANOV, AS
BRYCE, MR
HEATON, JN
MOORE, AJ
SKABARA, PJ
HOWARD, JAK
ORTI, E
VIRUELA, PM
VIRUELA, R
机构
[1] UNIV DURHAM,DEPT CHEM,DURHAM DH1 3LE,ENGLAND
[2] UNIV VALENCIA,DEPT QUIM FIS,E-46100 BURJASSOT,SPAIN
关键词
D O I
10.1039/jm9950501689
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The synthesis of the new mono- and di-functionalized tetrathiafulvalene (TTF) derivatives 4, 5 and 12-15 is reported. Compounds 4 and 5 have been studied in detail: their single crystal X-ray structures are reported and theoretical calculations at both semiempirical and ab initio levels have been performed. The TTF moiety in the crystal of 4 is folded, whereas in the crystal of 5 it is essentially planar. In the crystal structure of 4 the molecules related via an inversion centre form close dimers which pack in a severely distorted kappa-arrangement. Molecules of 5 assemble into uniform stacks with TTF moieties overlapping the side chains of adjacent molecules. Calculated geometries are in good agreement with the X-ray data, and the distortion from planarity in the crystal of 4 can be explained by nonbonding interactions between the amide substituent and the TTF rings of adjacent molecules. Evidence for intramolecular charge-transfer from the TTF ring to the electron-withdrawing amide and ester substituents of 4 and 5, respectively, is provided by UV-VIS spectroscopy in solution, analysis of the bond lengths in the crystal structure, and by theoretical calculations.
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页码:1689 / 1696
页数:8
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