Issue 12, 2019

Inverted energy gap law for the nonradiative decay in fluorescent floppy molecules: larger fluorescence quantum yields for smaller energy gaps

Abstract

A data survey on experimental fluorescence quantum yields of (multi)substituted dicyano-distyrylbenzenes in fluid solution evidences that non-radiative decay increases with the Franck–Condon energy (EFC), being opposite to the conventional energy gap law. Quantum-chemistry indicates that this is controlled by access to the conical intersection (CI) following the Bell–Evans–Polanyi principle as a first-step approximation for this family of molecules; the variations in EFC among the different compounds are found to be decisive, while those of ECI are estimated to be weaker or even enhancing the effect. The current findings may have significant consequences for the design of molecules for organic solid state emitters.

Graphical abstract: Inverted energy gap law for the nonradiative decay in fluorescent floppy molecules: larger fluorescence quantum yields for smaller energy gaps

Supplementary files

Article information

Article type
Research Article
Submitted
18 Feb 2019
Accepted
18 Apr 2019
First published
19 Apr 2019

Org. Chem. Front., 2019,6, 1948-1954

Inverted energy gap law for the nonradiative decay in fluorescent floppy molecules: larger fluorescence quantum yields for smaller energy gaps

J. Shi, M. A. Izquierdo, S. Oh, S. Y. Park, B. Milián-Medina, D. Roca-Sanjuán and J. Gierschner, Org. Chem. Front., 2019, 6, 1948 DOI: 10.1039/C9QO00259F

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