TY - JOUR
T1 - Improving Stability, Crystallinity, and Photo-Responsiveness of Supramolecular Frameworks by Surface Polymerization
AU - Yang, Tao
AU - Li, Xue-mei
AU - Liu, Yang
AU - Wei, Chao
AU - Zuo, Mingrui
AU - Guo, Tianyu
AU - Liu, Guoliang
AU - Ding, Lifeng
AU - Liu, Xiao-Qin
AU - Sun, Lin-Bing
N1 - Publisher Copyright:
© 2024 Wiley-VCH GmbH.
PY - 2024/7/1
Y1 - 2024/7/1
N2 - Metal–organic cage-based photo-responsive supramolecular frameworks (PSMFs) with permanent porosity have gained attention for their modular properties, controllable functionality, and light-induced reversible responsiveness. However, their high porosity and photo-responsive efficiency are often compromised due to poor structural stability upon solvent removal, limiting their potential applications. Here, a solution to overcome this challenge by employing a surface polymerization strategy using isophorone diisocyanate (IDI) to stabilize PSMF (PCC-20t) is presented. This approach results in the composite of PCC-20t@PolyIDI, which preserves crystallinity and permanent high-porosity while avoiding structural collapse commonly observed in highly porous supramolecular frameworks. Moreover, compared to activated PCC-20t, PCC-20t@PolyIDI exhibits an 18.6-fold increase in specific surface area. Remarkably, the structural variability of PCC-20t@PolyIDI can be observed in the photo-regulation behavior of CO 2 capacity under the irradiation of vis- and UV-light, showing a 27.9% change in adsorption amount for CO 2 which is significantly higher than that of the activated PCC-20t with 7.0% for CO 2. Grand Canonical Monte Carlo simulations demonstrate the light-regulated adsorption performance is attributed to the configuration transformation of azobenzene from trans- to buckling state. The findings may pave the way for stabilizing high-porosity materials to simultaneously meet demands for high-porosity and photo-responsive efficiency.
AB - Metal–organic cage-based photo-responsive supramolecular frameworks (PSMFs) with permanent porosity have gained attention for their modular properties, controllable functionality, and light-induced reversible responsiveness. However, their high porosity and photo-responsive efficiency are often compromised due to poor structural stability upon solvent removal, limiting their potential applications. Here, a solution to overcome this challenge by employing a surface polymerization strategy using isophorone diisocyanate (IDI) to stabilize PSMF (PCC-20t) is presented. This approach results in the composite of PCC-20t@PolyIDI, which preserves crystallinity and permanent high-porosity while avoiding structural collapse commonly observed in highly porous supramolecular frameworks. Moreover, compared to activated PCC-20t, PCC-20t@PolyIDI exhibits an 18.6-fold increase in specific surface area. Remarkably, the structural variability of PCC-20t@PolyIDI can be observed in the photo-regulation behavior of CO 2 capacity under the irradiation of vis- and UV-light, showing a 27.9% change in adsorption amount for CO 2 which is significantly higher than that of the activated PCC-20t with 7.0% for CO 2. Grand Canonical Monte Carlo simulations demonstrate the light-regulated adsorption performance is attributed to the configuration transformation of azobenzene from trans- to buckling state. The findings may pave the way for stabilizing high-porosity materials to simultaneously meet demands for high-porosity and photo-responsive efficiency.
KW - metal–organic cages
KW - photo-responsiveness
KW - polymerization
KW - porosity
KW - supramolecular frameworks
UR - http://www.scopus.com/inward/record.url?scp=85197447529&partnerID=8YFLogxK
U2 - 10.1002/adfm.202404869
DO - 10.1002/adfm.202404869
M3 - Article
SN - 1616-301X
JO - Advanced Functional Materials
JF - Advanced Functional Materials
M1 - 2404869
ER -