期刊
INORGANIC CHEMISTRY
卷 61, 期 6, 页码 2813-2823出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03203
关键词
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资金
- National Natural Science Foundation of China [92061201, 21825106]
- NSFC-Henan Joint Foundation [U2004190]
- Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province [19IRTSTHN022]
- Key Scientific and Technological Project of Henan Province [202102210027]
- innovation and entrepreneurship training program for college students in Henan Province [201910459170]
A new viologen-based metal-organic polyhedron material with reversible photochromic and electrochromic dual responsive behaviors has been successfully synthesized, showing high stability and short coloration times.
Stable stimulus-responsive materials are highly desirable due to their widespread potential applications and growing demand in recent decades. Despite the fact that viologen derivatives have long been known as excellent photochromic and electrochromic materials, the development of stable viologen-based multifunctional smart materials with short coloration times remains an exciting topic. To obtain photochromic and electrochromic dual responsive materials, embedding the viologen ligand into a robust metal oxide cluster to increase its stability and sensitivity is an effective strategy. Herein, a viologen-based metal-organic polyhedron (MOP) {[Zr6L3(mu(3)-O)(2)(mu(2)-OH)(6)Cp-6]center dot 8Cl center dot CH3OH center dot DMF} [Zr-MOP-1; H2L center dot 2Cl = 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium dichloride, and Cp = eta(5)-C5H5] was successfully prepared and characterized. It consists of trinuclear Zr-oxygen secondary building units and exhibits reversible photochromic and electrochromic dual responsive behaviors. As expected, the designed robust viologen-based nanocage with a V2E3 (V = vertex, and E = edge) topology can maintain its stability and rapid photo/electrochromic behaviors with an obvious reversible change in color from purple (brown) to green, mainly due to the enclosed cluster structure and the abundant free viologen radicals that originate from the effective Cl -> N and O -> N electron transfers. Spectroelectrochemistry and theoretical calculations of this Zr-MOP were also performed to verify the chromic mechanism.
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