Počet záznamů: 1
Toward designed singlet fission: Solution photophysics of two indirectly coupled covalent dimers of 1,3-diphenylisobenzofuran
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SYSNO ASEP 0393977 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Toward designed singlet fission: Solution photophysics of two indirectly coupled covalent dimers of 1,3-diphenylisobenzofuran Tvůrce(i) Johnson, J. C. (US)
Akdag, A. (US)
Zamadar, M. (US)
Chen, X. (US)
Schwerin, A. F. (US)
Paci, I. (US)
Smith, M. B. (US)
Havlas, Zdeněk (UOCHB-X) RID, ORCID
Miller, J. R. (US)
Ratner, M. A. (US)
Nozik, A. J. (US)
Michl, Josef (UOCHB-X) RID, ORCIDCelkový počet autorů 12 Zdroj.dok. Journal of Physical Chemistry B. - : American Chemical Society - ISSN 1520-6106
Roč. 117, č. 16 (2013), s. 4680-4695Poč.str. 16 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova density-functional theory ; intramolecular charge-transfer ; electron-transfer ; transfer excitations ; exciton fission Vědní obor RIV CF - Fyzikální chemie a teoretická chemie CEP GBP208/12/G016 GA ČR - Grantová agentura ČR Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 000318211600063 EID SCOPUS 84876758520 DOI 10.1021/jp310979q Anotace 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. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Viktorie Chládková, Tel.: 232 002 434 Rok sběru 2014
Počet záznamů: 1