Excitation Dynamics in Hetero-bichromophoric Calixarene Systems

Year: 2016

Authors: Tosi I., Centellas MS., Campioli E., Iagatti A., Lapini A., Sissa C., Baldini L., Cappelli C., Di Donato M., Sansone F., Santoro F., Terenziani F.

Autors Affiliation: Univ Parma, Dipartimento Chim, Parco Area Sci 17-A, I-43124 Parma, Italy; Scuola Normale Super Pisa, Piazza Cavalieri 7, I-56126 Pisa, Italy; LENS European Lab Non Linear Spect, Via N Carrara 1, I-50019 Sesto Fiorentino, FI, Italy;‎ INO, Largo Fermi 6, I-50125 Florence, Italy;‎ Univ Florence, Dipartimento Chim Ugo Schiff, Via Lastruccia 13, I-50019 Sesto Fiorentino, FI, Italy; UOS Pisa, CNR, ICCOM, Area Ric, Via G Moruzzi 1, I-56124 Pisa, Italy

Abstract: In this work, the dynamics of electronic energy transfer (EET) in bichromophoric donor-acceptor systems, obtained by functionalizing a calix[4] arene scaffold with two dyes, was experimentally and theoretically characterized. The investigated compounds are highly versatile, due to the possibility of linking the dye molecules to the cone or partial cone structure of the calix[4] arene, which directs the two active units to the same or opposite side of the scaffold, respectively. The dynamics and efficiency of the EET process between the donor and acceptor units was investigated and discussed through a combined experimental and theoretical approach, involving ultrafast pump-probe spectroscopy and density functional theory based characterization of the energetic and spectroscopic properties of the system. Our results suggest that the external medium strongly determines the particular conformation adopted by the bichromophores, with a direct effect on the extent of excitonic coupling between the dyes and hence on the dynamics of the EET process itself.

Journal/Review: CHEMPHYSCHEM

Volume: 17 (11)      Pages from: 1686  to: 1706

KeyWords: density functional calculations; donor-acceptor systems; energy transfer; solvent effects; ultrafast spectroscopy
DOI: 10.1002/cphc.201501065

Citations: 10
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