ISSN:
0947-6539
Keywords:
crystal engineering
;
hydrogen bonds
;
phosphonates
;
radical cations
;
tetrathia fulvalenes
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of Me3TTFLi (TTF = tetrathiafulvalene) with ClP(O)-(OEt)2 followed by hydrolysis with Me3SiBr affords the novel π-donor molecule trimethyltetrathiafulvalenylphosphonic acid (Me3TTF-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][Me3TTF-PO(OH)O-], which is described by analogy with the anti-CaSi2 structure type. Electrocrystallization of the former salt yields single crystals of a neutral (zwitterionic) π radical, formulated as [Me3TTF-PO(OH)O-]·+. 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 π-donor molecules of larger spatial extension. The analysis of the calculated HO-MO-HOMO intermolecular interaction energies demonstrates that these slabs contain strong π-π intermolecular interactions despite the nonexistence of any 2D network of short S ⃛S contacts. The spin susceptibility of [Me3TTF-PO-(OH)O-]·+, 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.
Additional Material:
13 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19960021015
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