Steric hindrances and spectral distributions affecting energy transfer rate: A comparative study on specifically designed donor-acceptor pairs
Authors: Domenichini E.; Doria S.; Di Donato M.; Cupellini L.; Biagiotti G.; Iagatti A.; Bussotti L.; Mennucci B.; Cicchi S.; Foggi P.
Autors Affiliation: University of Strasbourg, IPCMS, France; European Laboratory for Non Linear Spectroscopy (LENS), Universita’ Degli Studi di Firenze, Via Nello Carrara 1, Sesto Fiorentino, Florence, 50019, Italy; CNR-ICCOM, Consiglio Nazionale Delle Ricerche-Istituto-Istituto di Chimica Dei Composti OrganoMetallici, Via Madonna Del Piano 10, Sesto Fiorentino, Firenze, 50019, Italy; Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13, 56124, Pisa, Italy; Dipartimento di Chimica ”Ugo Schiff”, Università Degli Studi di Firenze, Via Della Lastruccia, 3-13, Sesto Fiorentino, Florence, 50019, Italy; CNR-INO, Consiglio Nazionale Delle Ricerche – Istituto Nazionale di Ottica, Largo Fermi 6, Florence, 50125, Italy; Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto 8, Perugia, 06100, Italy
Abstract: In this work the photophysics of four bichromophoric units was studied by means of static and time resolved spectroscopy, with the aim of disentangling the contribution of steric and electronic factors in regulating the efficiency of electronic energy transfer (EET). The newly synthesized dyads share the same acceptor moiety, a substituted BODIPY chromophore, and differ either in the donor or in the molecular bridge connecting the two units. The use of different linkers allows for tuning the conformational flexibility of the dyad, while changing the donor has an influence on the electronic coupling and spectral overlap between the two chromophores. The efficiency of energy transfer is extremely high in all the four dyads and can be modelled within the frame of the Förster equation. In the special case of a dimeric donor, a theoretical analysis was performed to further support the experimental findings. Geometry optimization at DFT level indicated that different conformations with similar energy can exist in solution, explaining the observed multi-exponential EET. Furthermore, energy transfer rates, computed at DFT level, resulted in optimal agreement with the experimental ones. Our analysis allowed to conclude that, in case of the studied systems, steric hindrance and donor-acceptor relative orientations plays a prominent role in regulating the EET dynamics, even overcoming electronic effects.
Journal/Review: DYES AND PIGMENTS
Volume: 174 Pages from: 108010-1 to: 108010-9
KeyWords: Non linear spectroscopy; dyad; chromophores; transient absorption; excited-state; bodipy; conversion; photodimerization; complexes; dynamics; solvent; dyesDOI: 10.1016/j.dyepig.2019.108010