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

Abstract

As promising photoresponsive materials and potential smart materials, hybrid photochromic materials (HPMs), especially for crystalline HPMs (CHPMs), have been broadly explored for their potential 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, the electron-transfer (ET) and crystal engineering strategies were utilized to predesign CHPMs with multiple photoresponsive properties via the collaboration of paramagnetic metal ion (Dy 3 + ), electron-donor (ED) ligand (benzene-1,2,3-tricarboxylic acid, H 3 BTA) and electron-acceptor (EA) ligand (1,10-phenanthroline, phen). The resulting complex [Dy(BTA)(phen) 2 ]•2H 2 O (1) shows hybrid chain with the intrachain Dy 3 + ions bridged and chelated by tricarboxylate and phen ligands, respectively. After photostimuli, the ET between tricarboxylate and phen results in photogenerated radicals and the resultant quadruple photoresponsive properties. Considering the abundant resources of paramagnetic metal ions, ED-and EA-ligands, this 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.

Lanthanide-based metal–organic framework materials as bifunctional fluorescence sensors toward acetylacetone and aspartic acid

“…18,19 In particular, the photoluminescence characteristics of Ln-MOFs expand the application in molecular switches and chemical sensors. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] Many Ln-MOFs have been applied to detect metal cations, inorganic anions and small organic molecules. 25,26 However, there are few reports of Ln-MOFs for the detection of amino acids.…”

Electron transfer photochromism of Ln-based (Ln = Dy, Tb) coordinated polymers for reversibly switching off/on single-molecule magnetic behavior

“…Recently, a Dy-based photochromic complex with photogenerated radical-actuated SMMs was realized in our previous work [30], showing the first example of SMMs in electron transfer photochromic materials. This motivates us to further explore the possibility of tunable SMMs via electron transfer photochromic complexes [32][33][34][35][36][37][38]. Especially, it is a challenging but interesting issue for switching off SMMs in these photochromic system.…”

Interpenetrated metal–organic frameworks with enhanced photoluminescence for selective recognition of m-xylene from xylene isomers

“…Notably, luminescence-based sensing technologies are truly remarkable given that the luminescent materials can efficiently and easily show a colorimetric response to stimuli compared with other transduction ones. [16][17][18][19] In addition, combined with a spectrophotometer, luminescent materials can be identified as sensing materials based on characteristic absorption and emission shifts. [20][21][22][23] Among the reported luminescent materials, luminescent metal-organic frameworks (LMOFs) have recently emerged as potential chemical sensors because of their superiorities of inherent crystallinity, designable structure, tunable pores, and multiple functionalizations.…”