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(μ3-O)2(μ2-OH)6Cp6]·8Cl·CH3OH·DMF} [Zr-MOP-1; H2L·2Cl = 1,1′-bis(4-carboxyphenyl)-4,4′-bipyridinium
dichloride, and Cp = η5-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.