Journal
NEW JOURNAL OF CHEMISTRY
Volume 44, Issue 36, Pages 15538-15548Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0nj03584j
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Electrocrystallization of TMTTF (tetramethyltetrathiafulvalene) in the presence of the dianionic [Pt(qS)(2)](2-)platinum complex (qS: 5-sulfo-8-quinolinol) afforded simultaneously two phases. Phase A with isolated dicationic (TMTTF)(2)(2+)species is fully insulating and characterized by C-H hydrogen bonds with the anionic sulfonate moieties. Phase B is a mixed valence salt formulated as (TMTTF)(3)[Pt(qS)(2)]. It is organized into strongly trimerized chains, with a notably higher conductivity (sigma(RT)= 4 x 10(-5)S cm(-1)). The charge distribution within the TMTTF trimers has been evaluated from the intramolecular bond distances, and IR and Raman spectra, converging all to a +0.5/+1/+0.5 motif, which is not modified at lower temperatures. Spectroscopic studies of such trimeric structures are scarce and the doublet (or triplet) structure expected in the IR of trimers is clearly identified here in the EMV-activated nu(8)(a(g)) mode associated with the totally symmetric vibration of methyl groups, in relation to the weak C-HMIDLINE HORIZONTAL ELLIPSISO hydrogen bonds between the radical cation and the dianionic [Pt(qS)(2)](2-)platinum complex.
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