Issue 6, 2012

A two-step ICT process for solvatochromic betaine pyridinium revealed by ultrafast spectroscopy, multivariate curve resolution, and TDDFT calculations

Abstract

This work deals with the photophysics of a pyridinium betaine, 2-pyridin-1-yl-1H-benzimidazole (SBPa), based on a combination of steady-state, femtosecond photoionization (gas phase) and femtosecond transient absorption (solution) spectroscopic measurements, supported by (LR)-PCM-(TD)DFT calculations. Preliminary and new electrochemical results have revealed a strongly negative solvatochromic charge transfer (CT) absorption due to a S0 → S2 vertical transition and a weakly-solvatochromic emission due to S1 → S0 transition. Advanced TDDFT optimizations of the Franck–Condon states S2(FC) and S1(FC) led to two additional CT levels with planar geometry, S2(CT) and S1(CT), respectively, allowing prediction of a two-step photoinduced ICT process, i.e., S0 → S2(FC) and S2(CT) → S1(CT), separated by a S2(FC) → S2(CT) back charge transfer relaxation. While the pyridinium ring is the acceptor group in both steps, two different donor groups, the benzene ring and the imidazole bridge, are involved in the excitation and internal conversion processes, respectively. Femtosecond transient absorption experiments supported by MCR-ALS decomposition confirmed indeed the contribution of two distinct CT states in the photophysics of SBPa: following excitation to the S2(CT) state, ultrafast production of the emissive S1 state (the only channel observable in the gas phase) was observed to occur in competition with a further ICT process toward the S1(CT) state, with a time constant ranging from 300 fs to 20 ps depending on the solvent. While in aprotic media this ICT process was found to be purely solvent controlled (double polarity and viscosity dependency), in protic solvents, the influence of the hydrogen bond network has to be taken into account. Comparison with data obtained for a pre-twisted SBPa analogue led us to exclude the presence of any large-amplitude geometrical change during ICT. Analyzing the solvent dependency using the power law approach, we concluded that the S1(CT) state decays essentially through IC in the 3–40 ps time range whereas the emissive S1 state decays within 130–260 ps via IC, ISC and fluorescence.

Graphical abstract: A two-step ICT process for solvatochromic betaine pyridinium revealed by ultrafast spectroscopy, multivariate curve resolution, and TDDFT calculations

Supplementary files

Article information

Article type
Paper
Submitted
11 Jul 2011
Accepted
30 Nov 2011
First published
09 Jan 2012

Phys. Chem. Chem. Phys., 2012,14, 1945-1956

A two-step ICT process for solvatochromic betaine pyridinium revealed by ultrafast spectroscopy, multivariate curve resolution, and TDDFT calculations

S. Aloïse, Z. Pawlowska, C. Ruckebusch, M. Sliwa, J. Dubois, O. Poizat, G. Buntinx, A. Perrier, F. Maurel, P. Jacques, J. Malval, L. Poisson, G. Piani and J. Abe, Phys. Chem. Chem. Phys., 2012, 14, 1945 DOI: 10.1039/C2CP22254J

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