Modulating the Photophysical Properties and Electron Transfer Rates in Diketopyrrolopyrrole-Based Coordination Polymers.

Molecular self-assembly through noncovalent interactions is a particularly efficient approach to fine-tune the optoelectronic and photophysical properties of electroactive materials. In metal-ligand coordination polymers, the final properties of the assemblies are directly related to the nature of the metal-ligand interaction. To probe for such influence on the photophysical properties of electroactive materials, a series of coordination polymers based on a well-known organic dye, diketopyrrolopyrrole, was prepared through coordination of a terpyridine-containing monomer with various metal sources, including iron, cobalt, zinc, and manganese. The resulting supramolecular polymers were characterized through multiple techniques, including UV-vis and fluorescence spectroscopy, time-correlated single-photon counting, and femtosecond transient absorption spectroscopy to reveal the impact of the metal source on the final photophysical properties of coordination polymers. As expected, important variations were found between different coordination polymers in terms of absorption, fluorescence kinetics, and electron transfer rate. While iron and cobalt-containing polymers showed ultrafast electrons transfer rates, assemblies from manganese were shown to be much less efficient, confirming the importance of metal centers. This detailed fundamental study unravels some important relationships between metal-ligand interactions, supramolecular self-assembly, and photophysical properties, ultimately leading to new avenues for the design of functional polymers based on organic dyes.