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Photo Switchable Two-step Photochromism in a Series of Ln-Phosphonate(Ln=Dy,Gd,Tb,Y)Dinuclear Complexes

Chemical Research in Chinese Universities 2022年第1期38卷 58-66页

作者： HU Ji-Xiang ZHANG Qian XIA Bin LIU Tao PANG Jiandong BU Xian-He School of Materials Science and Engineering Nankai UniversityTianjin 300350P.R.China College of Chemistry and Chemical Engineering Qingdao UniversityShandong 266071P.R.China State Key Laboratory of Fine Chemicals Dalian University of TechnologyDalian 116024P.R.China

Exploring the discrete complexes with multi-step coloration is still a challenge in the field of electron transfer photochromic materials. Herein, we synthesized a series of dinuclear Ln-diphosphonate compounds[Ln=Dy(1);Gd(2);Tb(3);Y(4)] with a remarkably and reversibly photoactive coloration phenomenon. These compounds showed two-step coloration behavior, which were the first discrete architectures in the reported electron transfer photochromic complexes. This two-step coloration phenomenon was originated from the large distortion of H3-TPT acceptors, which in turn reduced the π-conjugation of electron acceptors and slowed the decay process of electron transfer. The photogenerated stable doublet radicals originated from electron transfer from diphosphonate donor to polypyridine acceptor in these complexes were detected by UV-Vis and electron spin resonance(ESR) spectra. Furthermore, the photogenerated radicals were estimated by direct current magnetic susceptibilities and variable temperature ESR spectra, suggesting the doublet radicals in the dinuclear structure for all the compounds. This work revealed a series of discrete phosphonate-based systems with a multi-step coloration process, providing a new pathway for designing multicolor photochromic materials with potential photoswitching or other applications.

关键词： Discrete structure Donor-acceptor system doublet radical Photomagnetism Two-step photochromism

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