Perylenediimide-Based Donor–Acceptor MOF for Sunlight-Driven Photocatalytic <i>N</i>-α-C(sp<sup>3</sup>)–H Bond Functionalization of Tetrahydroisoquinoline
Hongjiu Liang, Junyan Wang, Lingtao Kong, Yuyan Shuai, J Chen, Xiaobo Li, Zhengfen Liu, Jian‐Jun Liu
Abstract
Sequential assembly of donor–acceptor components at the molecular level within a MOF is an effective strategy to achieve efficient electron–hole separation for enhancing the activity of photocatalysts. Meanwhile, the highly efficient and selective functionalization of tetrahydroisoquinoline (THIQ) under mild conditions remains an urgent demand in both the scientific and industrial communities. This work reports a donor–acceptor MOF photocatalyst ( PDI-MOF ) constructed by the coordinated assembly of donor and acceptor components, in which a naphthalene unit serves as an electron donor and a perylenediimide unit as an electron acceptor. The PDI-MOF can undergo rapid photoinduced electron transfer and exhibits long-lived charge-separated states with prominent photochromism. The photogenerated charges can rapidly activate the substrates THIQ and O 2, thereby achieving a highly selective coupling reaction of the C–C and C–P bonds of THIQ. In addition to the gram-scale reaction, PDI-MOF can also be applied to conduct photocatalytic reactions under natural sunlight and ambient air, highlighting its prospects for industrial application.