Me(3)TTF-PO3H2, a redox phosphonic acid and its monoanilinium salt [PhNH(3)(+)][Me(3)TTF-PO(OHO-], the electrocrystallized neutral (zwitterionic) pi radical [Me(3)TTF-PO(OHO-](.+), and their associated lamellar constructions in the solid state

被引:40
作者
Dolbecq, A
Fourmigue, M
Krebs, FC
Batail, P
Canadell, E
Clerac, R
Coulon, C
机构
[1] UNIV NANTES,INST MAT,CNRS,UMR 110,F-44072 NANTES,FRANCE
[2] UNIV PARIS 11,PHYS SOLIDES LAB,CNRS,UA 2,F-91405 ORSAY,FRANCE
[3] CSIC,INST CIENCIA MAT,BELLATERRA 08193,SPAIN
[4] UNIV PARIS 11,CHIM THEOR LAB,CNRS,UA 506,F-91405 ORSAY,FRANCE
[5] CNRS,CTR RECH PAUL PASCAL,F-33600 PESSAC,FRANCE
关键词
crystal engineering; hydrogen bonds; phosphonates; radical cations; tetrathiafulvalenes;
D O I
10.1002/chem.19960021015
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction of Me(3)TTFLi (TTF = tetrathiafulvalene) with CIP(O)-(OEt)(2) followed by hydrolysis with Me(3)SiBr affords the novel pi-donor molecule trimethyltetrathiafulvalenylphosphonic acid (Me(3)TTF-PO3H2) in a partially oxidized form. Subsequent reduction and neutralization with aniline gives the corresponding phosphonate monoanilinium salt. A unique hydrogen-bonded hexagonal net is identified within the lamellar structure of [PhNH(3)(+)][Me(3)TTF-PO(OHO-], which is described by analogy with the anti-CaSi2 structure type. Electrocrystallization of the former salt yields single crystals of a neutral (zwitterionic) pi radical, formulated as [Me(3)TTF-PO(OHO-](.+). Their structure reveals the presence of hydrogen-bonded molecular ribbons whose association creates a novel layered architecture similar to that obtained within radical cation salts of pi-donor molecules of larger spatial extension. The analysis of the calculated HO-MO-HOMO intermolecular interaction energies demonstrates that these slabs contain strong pi-pi intermolecular interactions despite the nonexistence of any 2D network of short S ... S contacts. The spin susceptibility of [Me(3)TTF-PO-(OHO-](.+), determined by single-crystal ESR measurements, is characteristic of triplet excitons, the origin of which may be understood from the electronic structure of the compound.
引用
收藏
页码:1275 / 1282
页数:8
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