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Me 3 TTF–PO 3 H 2 , a Redox Phosphonic Acid and Its Monoanilinium Salt [PhNH +3 ][Me 3 TTF–PO(OH)O ‐ ], the Electrocrystallized Neutral (Zwitterionic) π Radical [Me 3 TTF–PO(OH)O ‐ ] ·+ , and Their Associated Lamellar Constructions in the Solid State
Author(s) -
Dolbecq Anne,
Fourmigué Marc,
Krebs Frederik C.,
Batail Patrick,
Canadell Enric,
Clérac Rodolphe,
Coulon Claude
Publication year - 1996
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19960021015
Subject(s) - tetrathiafulvalene , chemistry , crystallography , intermolecular force , molecule , hydrogen bond , crystal structure , salt (chemistry) , redox , single crystal , lamellar structure , stereochemistry , inorganic chemistry , organic chemistry
The reaction of Me 3 TTFLi (TTF = tetrathiafulvalene) with ClP(O)‐(OEt) 2 followed by hydrolysis with Me 3 SiBr affords the novel π‐donor molecule trimethyltetrathiafulvalenylphosphonic acid (Me 3 TTF–PO 3 H 2 ) 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(OH)O ‐ ], which is described by analogy with the anti‐CaSi 2 structure type. Electrocrystallization of the former salt yields single crystals of a neutral (zwitterionic) π radical, formulated as [Me 3 TTF–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 [Me 3 TTF–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.