Push-Pull Bithienyl Chromophore with an Unusual Transverse Path of Conjugation

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• 作者：Rocí ; o Ponce Ortiz ; Reyes Malavé ; Osuna ; Ví ; ctor Herná ; ndez ; Juan T. L&oacute ; pez Navarrete ; Barbara Vercelli ; Gianni Zotti ; Ví ; ktor V. Sumerin ; Elizabeth S. Balenkova ; Va
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：February 8, 2007
• 年：2007
• 卷：111
• 期：5
• 页码：841 - 851
• 全文大小：509K
• 年卷期：v.111,no.5(February 8, 2007)
• ISSN：1520-5215

文摘

The synthesis, structure, and electronic properties of a novel cross-conjugated 10H-bisthienodithiocin-10-dicyanoethylene are reported. The X-ray single-crystal structure of the compound reveals a nonplanarconformation. The FT-IR and FT-Raman spectra of the compound show a great resemblance, which is aspectroscopic observation common to many push-pull systems. The UV-vis spectrum in CHCl₃ displays astrong absorption at 370 nm accompanied by a shoulder at 430 nm so that the optical gap is 2.88 eV. On theother hand, the electrochemical gap amounts to 2.38 V. DFT and TDDFT quantum chemical calculations, atthe B3LYP/6-31G** level, have been also performed to (i) determine the minimum-energy molecular structure,(ii) gain knowledge about the equilibrium atomic charges distribution, the topologies, and absolute energiesof the frontier molecular orbitals around the gap and about the molecular vibrations which give rise to themost outstanding Raman bands experimentally evidenced, and (iii) to analyze the nature of the vertical one-electron excitations associated to the strongest UV-vis absorptions.