Controlling π-Conjugated Polymer-Acceptor Interactions by Designing Polymers with a Mixture of π-Face Strapped and Nonstrapped Monomers.

Controlling π-conjugated polymer-acceptor complex interaction, including the interaction strength and location along the polymer backbone, is central to organic electronics and energy applications. Straps in the strapped π-conjugated polymers mask the π-face of the polymer backbone and hence are useful to control the interactions of the π-face of the polymer backbone with other polymer chains and small molecules compared to the conventional pendant solubilizing chains. Herein, we have synthesized a series of strapped π-conjugated copolymers containing a mixture of strapped and nonstrapped comonomers to control the polymer-acceptor interactions. Simulations confirmed that the acceptor is directed toward the nonstrapped repeat unit. More importantly, strapped copolymers overcome a major drawback of homopolymers and display higher photoinduced photoluminescence (PL) quenching, which is a measure of electron transfer from the polymer to acceptor, compared to that of both the strapped homopolymer and the conventional polymer with pendant solubilizing chains. We have also shown that this strategy applies not only to strapped polymers, but also to the conventional polymers with pendant solubilizing chains. The increase in PL quenching is attributed to the absence of a steric sheath around the comonomers and their random location along the polymer backbone, which enhances the probability of non-neighbor acceptor binding events along the polymer backbone. Thus, by mixing insulated and noninsulated monomers along the polymer backbone, the location of the acceptor along the polymer backbone, polymer-acceptor interaction strength, and the efficiency of photoinduced charge transfer are controllable compared to the homopolymers.