Boosting Ultrafast Trans‐Cis Photoisomerization and Intersystem Crossing in Nanocrystals of Double‐Bond Photoswitching Molecules

Author:

Pang Junhong1,He Jiaxing1,Deng Ziqi2,Chen Wenbin1,Chen Shunli1,Ni Shaofei1,Phillips David Lee2,Dong Zhengya3,Dang Li1,Li Ming‐De1ORCID

Affiliation:

1. College of Chemistry and Chemical Engineering Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province Shantou University Shantou 515063 China

2. Department of Chemistry The University of Hong Kong Pokfulam Road Hong Kong China

3. Chemistry and Chemical Engineering Guangdong Laboratory Shantou 515031 China

Abstract

AbstractDouble‐bond photoswitching molecules typically can undergo transcis photoisomerization, but their photoisomerization mechanisms in the solid state have been rarely reported. Herein, the excited‐state evolutions of trans‐azobenzene (AB), trans‐stilbene (TS), and N‐benzylideneaniline (NBA) are studied to unveil the relationship between the double‐bond photoswitching molecules and the photoisomerization kinetics in the solution phase and in nanocrystal suspensions (NCS). The photoisomerization rate of NBA is the fastest among these three molecules in the solution phase due to its most apparent single‐bond feature of the central double bond in the S1 state. The free space ordered crystal configuration boosts the photoisomerization rates of AB and TS in NCS to be faster than that of the solution phase because the hindrance of the wrapping solvent is eliminated in the crystals. In contrast, when NBA is prepared into NCS, it becomes distorted into a nonplanar structure because of the asymmetrical C‐H···π interactions, resulting in NBA having a large spin‐orbital coupling (SOC) value which opens the intersystem crossing channel to generate the triplet state instead of undergoing photoisomerization in solution. Therefore, this work reveals that the crystal configuration and the molecular structure may critically determine the photophysical properties of photoswitching materials.

Funder

National Natural Science Foundation of China

Department of Education of Guangdong Province

Publisher

Wiley

Subject

Atomic and Molecular Physics, and Optics,Electronic, Optical and Magnetic Materials

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