Enhancing energy transfer through visible-light-driven polymerization in a metal–organic framework

Abstract

In recent years, advances in novel photosensitive materials have been expected to drive the development of next-generation smart devices, especially in the field of high visible-light utilization. Limited by synthetic techniques, the development of sensitive photoresponsive materials driven by visible light has been slow, especially as the distribution of strictly ordered photoresponsive groups cannot be solved. Here, we report the synergistic construction of a photosensitive metal–organic framework (MOF) consisting of uniform photoresponsive groups. By means of two photoactive units and D–A–D characteristics, short-range photo-generated electron transfer (PET) efficiency is ensured; by virtue of lophine, radical-induced photochromism is generated; thanks to the spatial confinement effect of Zr-MOF and the affinity of the anthracene ring toward singlet oxygen, unlike the previously reported dimerization reaction, the photochemical polymerization of adjacent anthracene rings can be monitored via SCXRD, clearly illustrating the detailed mechanism of visible-light-etching at the nanoscale. The occurrence of polymerization not only induces a contraction of the framework, but also improves the long-range PET and overall photon utilization, which is also demonstrated by the effective photocatalytic activation of C(sp³)–H and construction of C–N. The related results demonstrate that exploiting the structural tailoring of MOF can provide valuable insights into the development of highly sensitive visible-light-driven lithography designs.