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DFT/TDDFT, NPA, and AIM-based study of the molecular switching properties of photocyclization and metallochromism of the DAE complexes

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Abstract

Diarylethene (DAE), the ubiquitous photochromic unit, is one of the most promising candidates for well-recognized optoelectronic applications. In this paper, the relationship between reversible photoisomerization/metallochromic properties and second-order nonlinear optical (NLO) responses for a new photochromism based on DAE with a benzyl-linked 8-aminoquinoline-2-aminomethylpyridine unit (1O) has been systematically investigated by using density functional theory. Our results show that closed-ring (1C) comprising DAE unit was shown to be capable of exhibiting both large static first hyperpolarizabilities βtot (1.075 × 10−28 esu) and large switch ratio βratio ~ 31 with corresponding open-ring because of the better delocalization of the π-electron system, the more obvious degree of charge transfer and the smaller transition energy in the closed-ring. When the metal ions have been injected in open-ring (1O*M), we observed a larger NLO response compared with the corresponding open-ring 1O. However, it can slightly decrease the βtot values in 1C*M. Natural bonding orbital and atom in molecules analysis provide a better understanding for the property differences in metallochromic process. We hope this research would be beneficial for further theoretical and experimental studies on large second-order NLO switches applications.

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Acknowledgements

The authors gratefully acknowledge the financial support from the “12th Five-Year” Science and Technology Research Project of the Education Department of Jilin Province ([2016] 494) and the National Natural Science Foundation of China (No. 21173035).

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Authors and Affiliations

  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China

    Jinting Ye, Li Wang, Hongqiang Wang, Xiumei Pan, Haiming Xie & Yongqing Qiu

  2. National and Local United Engineering Laboratory for Power Battery, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China

    Xiumei Pan, Haiming Xie & Yongqing Qiu

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  1. Jinting Ye
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Correspondence to Yongqing Qiu.

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214_2018_2204_MOESM1_ESM.doc

Supplementary material: The AIM Parameters of the ring-closed metal cation complexes 1C*M; The relationship of distances and the corresponding Wiberg indices, the tensorial components of first hyperpolarizabilities (10−30 esu), total first hyperpolarizabilities (10−30 esu) for 1O/1C and the metal cations complexes 1O*M and 1C*M; Molecular orbitals and absorption spectra of 1O*M/1C*M (M = Ni2+, Zn2+, Hg2+ and Pb2+) complexes. (DOC 6640 kb)

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Ye, J., Wang, L., Wang, H. et al. DFT/TDDFT, NPA, and AIM-based study of the molecular switching properties of photocyclization and metallochromism of the DAE complexes. Theor Chem Acc 137, 22 (2018). https://doi.org/10.1007/s00214-018-2204-5

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