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Polar Thiazole Derivative-Induced Second Harmonic Response in Hybrid Bismuth Chlorate with Reversible Photochromism.

Inorg Chem

October 2024

Key Laboratory of Chemical Sensing & Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan, Shandong250022, P. R. China.

Inorganic-organic hybrid bismuth halides demonstrate great prospect in the field of second-order nonlinear optical (NLO) crystals because the ns electron on Bi(III) could lead to large molecular polarization and high second harmonic generation (SHG) coefficient on a noncentrosymmetric structure. However, researchers cannot yet control the effective arrangements of the bismuth halide functional motif, which results in SHG-active hybrid bismuth halides being rare. Herein, thiazole derivatives with a polar donor-π-acceptor system are designed to explore hybrid bismuth halide NLO crystals.

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At present, viologen-based compounds can undergo reversible chemical/physical changes under external stimuli such as light and electricity. This makes these compounds have potential applications in smart windows, displays, and sensors. In order to obtain such materials, three viologen-POM inorganic-organic hybrid compounds have been successfully synthesized by a hydrothermal method, namely {[Cu(cybpy)(α-PWO)}·18HO (1), (Hbpy)·(cybpy)·[H(α-PWO)]}·32HO (2) and {(Hcybpy)(β-MoO)}·2HO (3) (cybpy·Br = 1-cyclobutylmethyl-[4,4']bipyridinyl-1-ium bromide, bpy = 4,4'-bipyridine).

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Inorganic-organic hybrid materials are a kind of multiduty materials with high crystallinity and definite structures, built from functional inorganic and organic components with highly tunable photochemical properties. Perylenediimides (PDIs) are a kind of strong visible light-absorbing organic dyes with π-electron-deficient planes and photochemical properties depending on their micro-environment, which provides a platform for designing tunable and efficient hybrid photocatalytic materials. Herein, four radical-doped PDI-based crystalline hybrid materials, Cl-PDI⋅SiWO (1), Cl-PDI⋅SiMoO (2), Cl-PDI⋅PWO (3), and Cl-PDI⋅PMoO (4), were attained by slow diffusion of polyoxometalates (POMs) into acidified Cl-PDI solutions.

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Article Synopsis
  • Reducing the dark current in photodetectors can boost their detection sensitivity, but it’s complicated and costly due to the need for precise material and process control.* -
  • This study introduces a new photochromic semiconductor made from a single component, which combines a viologen zwitterion with an inorganic framework, enhancing its performance.* -
  • After UV light exposure, the material changes color from yellow to green and experiences a significant drop in conductivity (by 14.6 times), leading to a doubling of photodetection sensitivity due to increased band gap and formation of excitons.*
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Photochromic Polyoxoniobates with Photoinduced "D-f-A" Electron Transfer Mechanism.

Angew Chem Int Ed Engl

June 2023

Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated Materials, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, China.

Compounds with redox activities have appealing applications in catalytic, electronic and magnetic properties, but the redox inert of polyoxoniobates (PONbs) significantly limits their applications for a long time. In this work, we are able to integrate organophosphate and lanthanide cluster into PONb to create the first family of inorganic-organic hybrid organophosphate-Ln-PONb composite clusters. These novel species not only present the first family of redox active PONbs that can be reduced to form long-lived "heteropoly blues" under ambient conditions, but also a new photochromic system.

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