title: Excitation Dynamics in Hetero-bichromophoric Calixarene Systems.
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.
authors: Dipartimento di Chimica, Università di Parma, Parco Area delle Scienze 17/a, 43124, Parma, Italy.
authors: Irene
authors: I
authors: Tosi
authors: Scuola Normale Superiore, Piazza dei Cavalieri 7, I-56126, Pisa, Italy.
authors: Mireia
authors: M
authors: Segado Centellas
authors: Dipartimento di Chimica, Università di Parma, Parco Area delle Scienze 17/a, 43124, Parma, Italy.
authors: Elisa
authors: E
authors: Campioli
authors: LENS (European Laboratory for Non Linear Spectroscopy), via N. Carrara 1, 50019, Sesto Fiorentino (FI), Italy.|INO (Istituto Nazionale di Ottica), Largo Fermi 6, 50125, Firenze, Italy.
authors: Alessandro
authors: A
authors: Iagatti
authors: LENS (European Laboratory for Non Linear Spectroscopy), via N. Carrara 1, 50019, Sesto Fiorentino (FI), Italy.|Dipartimento di Chimica "Ugo Schiff", Università di Firenze, via della Lastruccia 13, 50019, Sesto Fiorentino (FI), Italy.
authors: Andrea
authors: A
authors: Lapini
authors: Dipartimento di Chimica, Università di Parma, Parco Area delle Scienze 17/a, 43124, Parma, Italy.
authors: Cristina
authors: C
authors: Sissa
authors: Dipartimento di Chimica, Università di Parma, Parco Area delle Scienze 17/a, 43124, Parma, Italy. laura.baldini@unipr.it.
authors: Laura
authors: 0000-0002-0985-4331
authors: L
authors: Baldini
authors: Scuola Normale Superiore, Piazza dei Cavalieri 7, I-56126, Pisa, Italy. chiara.cappelli@sns.it.
authors: Chiara
authors: C
authors: Cappelli
authors: LENS (European Laboratory for Non Linear Spectroscopy), via N. Carrara 1, 50019, Sesto Fiorentino (FI), Italy. didonato@lens.unifi.it.|INO (Istituto Nazionale di Ottica), Largo Fermi 6, 50125, Firenze, Italy. didonato@lens.unifi.it.|Dipartimento di Chimica "Ugo Schiff", Università di Firenze, via della Lastruccia 13, 50019, Sesto Fiorentino (FI), Italy. didonato@lens.unifi.it.
authors: Mariangela
authors: 0000-0002-6596-7031
authors: M
authors: Di Donato
authors: Dipartimento di Chimica, Università di Parma, Parco Area delle Scienze 17/a, 43124, Parma, Italy.
authors: Francesco
authors: 0000-0003-0531-9865
authors: F
authors: Sansone
authors: CNR-Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organo Metallici (ICCOM-CNR), UOS di Pisa, Area della Ricerca via G. Moruzzi 1, I-56124, Pisa, Italy.
authors: Fabrizio
authors: F
authors: Santoro
authors: Dipartimento di Chimica, Università di Parma, Parco Area delle Scienze 17/a, 43124, Parma, Italy. francesca.terenziani@unipr.it.
authors: Francesca
authors: F
authors: Terenziani
keywords: density functional calculations; donor-acceptor systems; energy transfer; solvent effects; ultrafast spectroscopy