Despite the excellent photodynamic and photothermal properties of organic molecular photosensitizers (PSs) and photothermal agents (PTAs), such as porphyrin and naphthalocyanine, their poor water solubility severely impedes their biological applications. Covalent organic frameworks (COFs), as an emerging class of organic crystalline porous materials, possess free active end groups (bonding defects) and large inner pores, which make them an ideal type of nanocarriers for loading hydrophobic organic molecular PSs and PTAs by both bonding defect functionalization (BDF) and guest encapsulation approaches to obtain multifunctional nanomedicines for PDT/PTT combination therapy. In this work, we report a nanoscale COF (NCOF) prepared via a facile synthetic approach under ambient conditions. Furthermore, a dual-modal PDT/PTT therapeutic nanoagent, VONc@COF-Por (3), is successfully fabricated by stepwise BDF and guest encapsulation processes. The covalently grafted porphyrinic PS (Por) and the noncovalently loaded naphthalocyanine PTA (VONc) are independently responsible for the PDT and PTT functionalities of the nanoagent. Upon visible (red LED) and NIR (808 nm laser) irradiation, VONc@COF-Por (3) displayed high 1O2 generation and photothermal conversion ability (55.9%), consequently providing an excellent combined PDT/PTT therapeutic effect on inhibiting MCF-7 tumor cell proliferation and metastasis, which was well evidenced by in vitro and in vivo experiments. We believe that the results obtained herein can significantly promote the development of NCOF-based multifunctional nanomedicines for biomedical applications.

Postsynthetic modification (PSM) has been demonstrated to be a powerful method for achieving new covalent organic frameworks (COFs) via single-step or multistep organic functional group transformations on established COF frameworks. PSM, however, might sometimes lead to collapse of the COF framework, decreases in crystallinity, or low postsynthetic yield due to the inherent limit of solid-state synthesis. Herein we report, for the first time, a new synthetic strategy that can generate new COFs via multicomponent one-pot in situ reactions. In total, 12 α-aminonitrileand quinoline-linked COFs with high crystallinity and permanent porosity are successfully achieved by three-component one-pot in situ Strecker and Povarov reactions under solvothermal conditions in high yields. The obtained COFs feature the same structures as those obtained from the stepwise PSM approach on an established imine-linked COF. This in situ multicomponent assembly strategy, as a synthetic methodology parallel to PSM, might open a new route for constructing COFs that is not possible under PSM conditions.

In this review, a comprehensive summary of the potential photocatalytic applications realized to date in the fast-growing field of COFs is provided with the aim to present a full blueprint of COFs for photochemical energy conversion and reactions.

HIGHLIGHTS Covalent organic frameworks (COFs) are first used in tumor photodynamic therapy BODIPY-decorated COFs are synthesized via bonding defects functionalization BODIPY-decorated COFs have excellent anti-tumor efficacy in vitro and in vivo COFs show great promise as nanoplatforms for biomedical applications

A porous Cu(I)-MOF was constructed from CuI and 1-benzimidazolyl-3,5-bis(4-pyridyl)benzene. This Cu(I)-MOF can be a highly sensitive naked-eye colorimetric sensor to successively detect water and formaldehyde species in a single-crystal-to-single-crystal fashion. Solid-state guest-responsive luminescence is also used to monitor the sensing process.