Polyoxometalate-Zr-Organic Cage Hybrid Ionic Salts Exhibiting Rapid Photochromic Behavior

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Two hybrid ionic salts, {[Cp 3 Zr 3 μ 3 -O(μ 2 -OH) 3 ] 2 (C 6 H 10 O 4 ) 3 } 2 [PMo 12 ]·Cl· x Solvent ( ZrAAD-PMo 12 ) and {[Cp 3 Zr 3 μ 3 -O(μ 2 -OH) 3 ] 2 (C 6 H 10 O 4 ) 3 } 2 [SiMo 12 ]· x Solvent ( ZrAAD-SiMo 12 ), were successfully synthesized via the liquid–liquid diffusion method. They were assembled from presynthesized adipic acid-directed capsular zirconium-based metal–organic cages (ZrAAD) and Keggin-type heteropolymolybdates ([PMo 12 O 40 ] 3– and [SiMo 12 O 40 ] 4– ), respectively. Under visible light irradiation, the two hybrid salts exhibited fast and reversible photochromic behavior. Solid-state UV–vis spectra revealed new Mo 5+ characteristic peaks at 740 nm ( ZrAAD-PMo 12 ) and 725 nm ( ZrAAD-SiMo 12 ) upon light exposure, corresponding to reduction of Mo 6+ . Additionally, the EPR results further confirmed the presence of Mo 5+ ions after light irradiation. Furthermore, the plausible photochromic mechanism was proposed.

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