Toward designed singlet fission: Solution photophysics of two indirectly coupled covalent dimers of 1,3-diphenylisobenzofuran

0393977 - ÚOCHB 2014 RIV US eng J - Článek v odborném periodiku
Johnson, J. C. - Akdag, A. - Zamadar, M. - Chen, X. - Schwerin, A. F. - Paci, I. - Smith, M. B. - Havlas, Zdeněk - Miller, J. R. - Ratner, M. A. - Nozik, A. J. - Michl, Josef
Toward designed singlet fission: Solution photophysics of two indirectly coupled covalent dimers of 1,3-diphenylisobenzofuran.
Journal of Physical Chemistry B. Roč. 117, č. 16 (2013), s. 4680-4695. ISSN 1520-6106. E-ISSN 1520-5207
Grant CEP: GA ČR GBP208/12/G016
Institucionální podpora: RVO:61388963
Klíčová slova: density-functional theory * intramolecular charge-transfer * electron-transfer * transfer excitations * exciton fission
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 3.377, rok: 2013

In order to identify optimal conditions for singlet fission, we are examining the photophysics of 1,3-diphenylisobenzofuran (1) dimers covalently coupled in various ways. In the two dimers studied presently, the coupling is weak. The subunits are linked via the para position of one of the phenyl substituents, in one case (2) through a CH2 linker and in the other (3) directly, but with methyl substituents in ortho positions forcing a nearly perpendicular twist between the two joint phenyl rings. The measurements are accompanied with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. Although in neat solid state, 1 undergoes singlet fission with a rate constant higher than 10(11) s(-1); in nonpolar solutions of 2 and 3, the triplet formation rate constant is less than 10(6) s(-1) and fluorescence is the only significant event following electronic excitation. In polar solvents, fluorescence is weaker because the initial excited singlet state S-1 equilibrates by sub-nanosecond charge transfer with a nonemissive dipolar species in which a radical cation of 1 is attached to a radical anion of 1. Most of this charge transfer species decays to S-0, and some is converted into triplet T-1 with a rate constant near 10(8) s(-1). Experimental uncertainties prevent an accurate determination of the number of T-1 excitations that result when a single S-1 excitation changes into triplet excitation. It would be one if the charge-transfer species undergoes ordinary intersystem crossing and two if it undergoes the second step of two-step singlet fission. The triplet yield maximizes below room temperature to a value of roughly 9% for 3 and 4% for 2. Above similar to 360 K, some of the S-1 molecules of 3 are converted into an isomeric charge-transfer species with a shorter lifetime, possibly with a twisted intramolecular charge transfer (TICT) structure. This is not observed in 2.
Trvalý link: http://hdl.handle.net/11104/0222333