Synergistic modulation of steric hindrance and isomerization space for enhanced photo-regulated performance of metal-organic polyhedra
Shu Shi†, Mu-Yi Xu†, Yang Liu, Yu-Xia Li, Lin-Bing Sun*
Chin. J. Struct. Chem., 2026, 45(8), 100962. DOI: 10.1016/j.cjsc.2026.100962
August 1, 2026
Gas adsorption; Photo-regulated performance; Metal-organic polyhedra; Propylene/propane separation
ABSTRACT
As an emerging class of smart materials, photoresponsive metal–organic polyhedra (PMOPs) have garnered growing attention owing to their modular architectures, tunable functionality and remote addressability. However, severe aggregation in the solid state compromises the photoresponsiveness; additionally, their photo-regulated performances (e.g. on adsorption) remain to be improved. Here we report a synergistic modulation strategy that concurrently engineers steric hindrance and isomerization space to construct a novel Rh-based PMOP, (tBu-Azo)(LA)MOP. This cage architecture comprises a sterically hindered azobenzene unit (tBu-Azo) and a long alkyl-chain spacer (LA), where the tert-butyl groups are designed to enhance the manipulation on open metal sites, while the LA ligands are designed to provide essential intermolecular spacing for efficient photoisomerization. Upon visible-/UV-light irradiation, the photoresponsive units in (tBu-Azo)(LA)MOP undergo reversible trans–cis isomerization with markedly improved photo-regulated performance. Consequently, a 49.7% change in propylene uptake is achieved—far surpassing that of the comparator (Azo)MOP assembled from unmodified azobenzene ligands in the absence of LA (17.1%). The outstanding photo-regulated performance, combined with high adsorption capacity, positions (tBu-Azo)(LA)MOP among the top-performing photoresponsive adsorbents reported to date. Density-functional-theory calculations are consistent with the interpretation that the trans–cis isomerization may effectively modulates the binding strength between active sites and C3H6. This work offers a viable avenue for the design of high-performance photoresponsive materials with broad applicability.
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