Covalent organic frameworks (COFs) are organic porous materials with many potential applications, which very often depend on the presence of chemical functionality at the organic building blocks. Functionality that cannot be introduced into COFs directly via de novo syntheses can be accessed through post-synthetic modification (PSM) strategies. Current strategies for the post-synthetic modification of COFs involve (i) incorporation of a variety of active metal species by using metal complexation through coordination chemistry, (ii) covalent bond formation between existing pendant groups and incoming constituents and (iii) chemical conversion of linkages. (iv) The post-synthetic modification is sometimes assisted by a monomer truncation strategy for the internal functionalization of COFs. (v) Even more intriguing methods that go beyond PSM are herein termed building block exchange (BBE) which encompasses framework-to-framework transformations taking advantage of the fact that reversible bond formation is a characteristic feature of COFs. This strategy allows the use of protoCOF structures (i.e., the utilization of a parent COF as a template) for the evolution of new COF structures with completely new components.
This tutorial review surveys recent advances in the field of C60/π-conjugated oligomer donor–acceptor ensembles. In particular, different synthetic strategies are discussed that were developed to link π-conjugated oligomers, as versatile photoexcited state electron donors, to C60. We highlight relationships between the nature/structural aspects of π-conjugated donor systems and a variety of physico-chemical features. Modifications of the oligomeric components are discussed under aspects of tailoring (i) the absorption cross-section of the chromophore in the visible region, (ii) the oxidation potential of the oligomeric donor moiety, (iii) the size, shape, or chemical makeup of the oligomer, and (iv) the stabilization of the charge-separated radical ion pairs. In the final section, the applicability of selected materials for the fabrication of photovoltaic devices is analyzed.