To which sites were thiols added? Insight into the thiol-yne click-based post-synthetic modification of conjugated microporous polymers

A post-synthetic modification (PSM) strategy is useful for the functionalization of conjugated microporous polymers (CMPs). This work shows that the reactivities of chemical moieties in networks are different from those of the isolated molecule state. We suggest that the main chains of CMPs can be chemically inert and the existence of defects is actually critical in the main chain PSM of CMPs. In the thiol-yne click-based main chain PSM of CMPs, thiols were added to defect sites such as 1,3-diynes and dangling alkynes. We suggest that the network-induced resistance for structural strains is the reason for the chemical inertness of the main chains of CMPs. Thus, it can be noted that the unique defective feature of CMPs is beneficial for PSM-based functionalization. We suggest that 1,3-diynes are main reaction sites in the thiol-yne click-based main chain post-synthetic modification of conjugated microporous polymers.