Quadruple Photoresponsive Functionality in a Crystalline Hybrid Material: Photochromism, Photomodulated Fluorescence, Magnetism and Nonlinear Optical Properties.

As promising photoresponsive materials and potential smart materials, hybrid photochromic materials (HPMs), especially for crystalline HPMs (CHPMs), have been broadly explored for their potentiality in inheriting the merits of each constituents, and intriguing photomodulated functionality. Hitherto, the photoresponsive functionality in explored CHPMs mainly concentrate on dyad combination. By contrast, triple or quadruple photoresponsive properties are very rare because of the limited compatibility of multiple photoresponsive functionality in a single system. In this work, we utilize the electron-transfer (ET) and crystal engineering strategies to predesign CHPMs with multiple photoresponsive properties via the collaboration of paramagnetic metal ion (Dy3+), electron-donor (ED) ligand (benzene-1,2,3-tricarboxylic acid, H3BTA) and electron-acceptor (EA) ligand (1,10-phenanthroline, phen). The resulting complex [Dy(BTA)(phen)2]·2H2O (1) shows hybrid chain with the intrachain Dy3+ ions bridged and chelated by tricarboxylate and phen ligands, respectively. After photostimuli, the ET between tricarboxylate and phen gives birth to photogenerated radicals, resulting in the quadruple photoresponsive properties. Considering the abundant resources of paramagnetic metal ions, ED- and EA-ligands, our work provides a general method to construct CHPMs with multiple photoresponsive performances via the collaboration of each unit under the guidance of ET and crystal engineering strategies.