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Appending Diverse π‐Extended Acceptors with Tetrathiafulvalene/Dithiafulvalene Donors: Multistate Redox Properties, Radical Ion Generation, and Mid‐IR‐Absorbing Mixed‐Valence States
Author(s) -
Keshri Sudhir Kumar,
Asthana Deepak,
Chorol Sonam,
Kumar Yogendra,
Mukhopadhyay Pritam
Publication year - 2018
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.201704604
Subject(s) - tetrathiafulvalene , imide , chromophore , redox , solvatochromism , photochemistry , radical ion , chemistry , valence (chemistry) , molecule , acceptor , electrochemistry , coronene , ion , polymer chemistry , inorganic chemistry , organic chemistry , electrode , physics , condensed matter physics
Three classes of donor–acceptor (D–A) π‐extended chromophores ( 1 – 12 ) were synthesized through a phosphite‐mediated cross‐coupling reaction, in which the anhydride‐ or imide‐based π‐As and number of tetrathiafulvalene (TTF)/dithiafulvalene (DTF) Ds were systematically changed. Large π rings, such as benzoperylene and coronene, were integrated into the TTF/DTF unit, for the first time, to overcome their high insolubility. The anhydride and imide groups in the π acceptors can significantly alter the frontier orbitals and influence the optoelectronic properties. The D moieties allow the formation of radical cations (D .+ ) and the π‐extended A moieties aid the formation of radical anions (A .− ) by oxidation/reduction under ambient conditions. The molecules revealed UV/Vis/near‐IR absorption, fluorescence extending into the near‐IR region, and amphoteric electrochemical properties. Chromophores 10 and 12 show solvatochromism in a wide range of solvents. The π‐As with anhydride functionality allow easier electron uptake, relative to the imide groups, whereas the increasing number of D TTF/DTF units make them easy to oxidize. Interestingly, the trans ‐TTF‐fused molecules ( 1 , 6 , and 11 ) exhibited a mixed‐valence state in the mid‐IR region ( ν ˜ =5130–4000 cm −1 ). Moderate electron coupling between the redox centers is inferred to the compounds being of Robin–Day class II. The multistate redox activity along with panchromism and near‐/mid‐IR optical absorption of these systems can be attractive towards advanced switchable materials.