Chinese Journal of Applied Chemistry ›› 2017, Vol. 34 ›› Issue (9): 1024-1034.DOI: 10.11944/j.issn.1000-0518.2017.09.170160

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Multi-Functional Viologen-Based Eu(Ⅲ) Complex with Photoswitchable Luminescence, Nonlinear Optical Properties and Photovoltaic Activity

DU Xiangshaa,LI Haiyanga,LIU Henga,LI Genhenga,LI Linkea*(),ZANG Shuangquana*()   

  1. College of Chemistry and Molecular Engineering,Zhengzhou University,Zhengzhou 450001,China
  • Received:2017-05-16 Accepted:2016-06-30 Published:2017-08-31 Online:2017-08-31
  • Contact: LI Linke,ZANG Shuangquan
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21371153, No.20901070), Program for Science & Key Scientific and Technological Project of Henan Province(No.132102210411), Key Scientific Research Project Plan in Colleges and Universities of Henan Province(No.16A150045)


The solvothermal reaction of a viologen-functionalized aromatic dicarboxylate ligand 1-(3,5-dicarboxybenzyl)-4,4'-bipyridinium nitrate(H2L+NO-3) with Eu(Ⅲ) leads to the formation of a new metal-organic complex {[Eu(μ2-OH)(L)(HCO2)]·H2O}n(1), in which the formate anions come from the in situ decomposition of solvent dimethylformamide(DMF). Single-crystal X-ray analysis revealed that complex 1 has chirality and diaplays a two-dimensional layer structure. Complex 1 manifests fast photoresponsive and reversibile photochromic properties. It gives an eye-detectable color change from pale-yellow to dark green upon exposure to light, and the coloring/fading processes can repeat several cycles. The structural analysis demonstrated that the electrons transfer from carboxylate donors to viologen acceptor as well as the π••••π interaction offers reasonable electron-transfer pathways for the photochromic process. Interestingly, the synthesized solid-state chiral crystalline material not only exhibits tunable luminescence in response to light, but also shows photoswitching nonlinear optical(NLO) activity, and the second-harmonic generation(SHG) efficiency is approximately 3.8 times that of potassium dihydrogen phosphate(KDP) in the same particle size. Moreover, surface photovoltage spectroscopy(SPS) of complex 1 has been investigated and the result indicates it exhibits interesting photovoltaic activity.

Key words: multi-functional, viologen-based, Eu(Ⅲ) complex, photoswitchable luminescence, nonlinear optical properties, photovoltaic activity