4.7 Article

Low-Coordinate Erbium(III) Single-Molecule Magnets with Photochromic Behavior

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INORGANIC CHEMISTRY
卷 61, 期 41, 页码 16295-16306

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AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c01999

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  1. National Science Centre Poland [2019/35/O/ST5/00647]

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This study explores the structures and magnetic properties of photo-responsive magnets that can be controlled by visible light irradiation. The authors present two erbium(III)-based coordination systems, one trinuclear molecule and one 1D coordination chain, both showing slow dynamics of magnetization. The trinuclear compound exhibits immediate color change in response to near-UV irradiation, while the chain-like compound does not show significant signs of photoisomerization.
The structures and magnetic properties of photo-responsive magnets can be controlled or fine-tuned by visible light irradiation, which makes them appealing as candidates for ternary memory devices: photochromic and photomagnetic at the same time. One of the strategies for photoresponsive magnetic systems is the use of photochromic/photoswitchable molecules coordinated to paramagnetic metal centers to indirectly influence their magnetic properties. Herein, we present two erbium(III)-based c o o r d i n a t i o n s y s t e m s : a t r i n u c l e a r m o l e c u l e {[ErIII(BHT)3]3(dtepy)2}.4C5H12 (1) and a 1D coordination chain {[ErIII(BHT)3(azopy)}n center dot 2C5H12 (2), where the bridging photochromic ligands belong to the class of diarylethenes: 1,2-bis((2-methyl-5-pyridyl)thie-3-yl)perfluorocyclopentene (dtepy) and 4,4 '-azopyridine (azopy), respectively (BHT = 2,6-di-tert- butyl-4-methylphenolate). Both compounds show slow dynamics of magnetization, typical for single-molecule magnets (SMMs) as revealed by alternating current (AC) magnetic susceptibility measurements. The trinuclear compound 1 also shows an immediate color change from yellow to dark blue in response to near-UV irradiation. Such behavior is typical for the photoisomerization of the open form of the ligand into its closed form. The color change can be reversed by exposing the closed form to visible light. The chain-like compound 2, on the other hand, does not show significant signs of the expected trans-cis photoisomerization of the azopyridine in response to UV irradiation and does not appear to show photoswitching behavior.

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