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Title: Multidimensional structure conformation of persulfurated benzene for highly efficient phosphorescence
Authors: Wu, Hongwei
Baryshnikov, Glib V.
Kuklin, Artem
Minaev, Boris F.
Wu, Bin
Gu, Long
Zhu, Liangliang
Ågren, Hans
Zhao, Yanli
Keywords: Science::Chemistry
Issue Date: 2021
Source: Wu, H., Baryshnikov, G. V., Kuklin, A., Minaev, B. F., Wu, B., Gu, L., ... Zhao, Y. (2021). Multidimensional structure conformation of persulfurated benzene for highly efficient phosphorescence. ACS Applied Materials and Interfaces, 13(1), 1314–1322. doi:10.1021/acsami.0c16338
Journal: ACS Applied Materials and Interfaces
Abstract: It is a challenge to acquire, realize, and comprehend highly emissive phosphorescent molecules. Herein, we report that, using persulfurated benzene compounds as models, phosphorescence can be strongly enhanced through the modification of molecular conformation and crystal growth conditions. By varying the peripheral groups in these compounds, we were able to control their molecular conformation and crystal growth mode, leading to one- (1D), two- (2D), and three-dimensional (3D) crystal morphologies. Two kinds of typical molecular conformations were separately obtained in these crystals through substituent group control or the solvent effect. Importantly, a symmetrical 3,3-conformer exhibits that a planar central benzene ring prefers a 3D-type crystal growth mode, demonstrating high phosphorescence efficiency. Such outcome is attributed to the strong crystal protection effect of the 3D crystal and the bright global minimum (GM) boat-like T1 state of the symmetrical 3,3-conformer. The conformation studies further reveal small deformation of the inner benzene ring in both singlet and triplet states. The GM boat-like T1 state is indicated by theoretical calculations, which is far away from the conical intersection (CI) point between the S0 and T1 potential energy surfaces. Meanwhile, the small energy gap between S1 and T1 states and the considerable spin–orbit coupling matrix elements allow an efficient population of the T1 state. Combined with the crystal protection and conformation effect, the 3,3-conformer crystal shows high phosphorescence efficiency. The unsymmetrical 2,4-conformer conformation with the twisted central benzene ring leads to 1D or 2D crystal growth mode, which has a weak crystal protection effect. In addition, the unsymmetrical conformation has a dark GM T1 state that is very close to the T1–S0 CI point, implying an efficient nonradiative T1–S0 quenching. Thus, weak phosphorescence was observed from the unsymmetrical conformation. This study provides an insight for the development of highly emissive phosphorescent materials.
ISSN: 1944-8244
DOI: 10.1021/acsami.0c16338
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials and Interfaces, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Fulltext Permission: embargo_20220120
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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