Addressing Charge-Transfer and Locally-Excited States in a Twisted Biphenyl Push-Pull Chromophore |
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Authors: | Dr Elisa Campioli Dr Somananda Sanyal Dr Agnese Marcelli Dr Mariangela Di Donato Dr Mireille Blanchard-Desce Dr Olivier Mongin Prof Dr Anna Painelli Prof Dr Francesca Terenziani |
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Institution: | 1. Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Università di Parma, Parco Area delle Scienze 17/A, 43124 Parma, Italy;2. LENS, via N. Carrara 11, 50019 Sesto Fiorentino (FI), Italy;3. Univ. Bordeaux Institut des Sciences Moléculaires (CNRS UMR 5255), 33405 Talence, France;4. Univ Rennes CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35000 Rennes, France |
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Abstract: | We present the synthesis and spectroscopic characterization of a twisted push–pull biphenyl molecule undergoing photoinduced electron transfer. Steady-state and transient absorption spectra suggest, in this rigid molecular structure, a subtle interplay between locally-excited and charge-transfer states, whose equilibrium and dynamics is only driven by solvation. A theoretical model is presented for the solvation dynamics and, with the support of quantum chemical calculations, we demonstrate the existence of two sets of states, having either local or charge-transfer character, that only “communicate” thanks to solvation, which is the sole driving force for the charge-separation process. |
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Keywords: | electron transfer dual fluorescence solvation dynamics time-resolved spectroscopy theoretical modelling |
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