Ultrafast Intramolecular and Solvation Dynamics in 4,7-Bis (4,5-dibutylbenzo[1,2-b:4,3-b ‘]bisthiophene[1,2-b:4,3-b ‘]bisthiophen-2-yl)-2,1,3-benzothiadiazole
Authors: Patrizi B., Iagatti A., Abbondanza L., Bussotti L., Zanardi S., Salvalaggio M., Fusco R., Foggi P.
Autors Affiliation: Univ Firenze, European Lab Non Linear Spect LENS, Via Nello Carrara 1, I-50019 Florence, Italy; CNR, INO, Largo Fermi 6, I-50125 Florence, Italy; Eni Spa, Renewable Energy & Environm Phys Chem, Via Fauser 4, I-28100 Novara, Italy; Univ Perugia, Dipartimento Chim Biol & Biotecnol, Via Elce Sotto 8, I-06123 Perugia, Italy; Ist Chim Composti Organometall CNR ICCOM, Via Madonna Piano 10, I-50019 Sesto Fiorentino, Italy
Abstract: We report a combined approach of stationary and time resolved fluorescence measurements and ultraviolet-visible (UV-vis) transient absorption spectroscopy (TAS) along with ab initio calculations, which provide an overall picture of the dynamics occurring after excitation in a push-pull molecule, namely, 4,7-bis (4,5-dibutylbenzo-[1,2-b:4,3-b’]bisthiophene[1,2-b:4,3-blbisthiophen-2-y1)-2,1,3-benzo- thiadiazole. The analysis of the emission spectra in solvents-of different polarities reveals the presence of three conformers whose structures differ in the orientation of the 4,5-dibutylbenzo-bisthiophene groups and in their planarity with respect to the benzothiadiazole acceptor group. The Kawski method allows us to estimate the ground- and first-excited state dipole moments (mu(g) and mu(e)) for the three conformers. We find values of mu(e) similar for the three conformers and higher than the relative mu(g) values as can be expected from a push pull molecule undergoing a light-induced charge-transfer (CT) transition. UV-vis TAS in different solvents highlights the instantaneous (within our instrumental resolution) formation of a locally excited S-1 state (accompanied by a big change in the dipole moment with respect to S-0), which undergoes a rapid intramolecular CT (ICT) assisted by molecule planarization [planar ICT (PICT)]. The strong dipole-dipole interactions with the polarized solvent molecules stabilize the S-1 CT state that decays principally through fluorescence emission. Both PICT and solvation dynamics are responsible for the big Stokes’ shift characterizing the molecule, particularly in polar solvents. The fluorescence lifetimes are substantially longer in polar solvents, and also fluorescence quantum yields are higher in polar solvents. We conclude that the radiative relaxation time increases when molecular planarization of the S, emissive state takes place, and this condition is favored in polar solvents where local dipole-dipole interactions support the structural stabilization of the CT emissive state. In the poly(methyl methacrylate) matrix, the structural and solvation dynamics are strongly inhibited, leading to reduction of nonradiative processes and to shortening of the fluorescence relaxation time.
Journal/Review: JOURNAL OF PHYSICAL CHEMISTRY C
Volume: 123 (10) Pages from: 5840 to: 5852
KeyWords: CHARGE-TRANSFER; DUAL FLUORESCENCE; SOLAR-CELLS; ABSORPTION; ENERGIES; DESIGN; FLUOROPHORES; RELAXATION; SHIFTSDOI: 10.1021/acs.jpcc.8b11191Citations: 11data from “WEB OF SCIENCE” (of Thomson Reuters) are update at: 2022-05-15References taken from IsiWeb of Knowledge: (subscribers only)Connecting to view paper tab on IsiWeb: Click hereConnecting to view citations from IsiWeb: Click here