Stable organic semiconductors (OSCs) with a high-spin ground-state can profoundly impact emerging technologies such as organic magnetism, spintronics, and medical imaging. Over the last decade, there has been a significant effort to design π-conjugated materials with unpaired spin centers. Here, we report new donor-acceptor (D-A) conjugated polymers comprising cyclopentadithiophene and cyclopentadiselenophene donors with benzobisthiadiazole (BBT) and iso-BBT acceptors. Density functional theory calculations show that the BBT-based polymers display a decreasing singlet–triplet energy gap with increasing oligomer chain length, with a degenerate singlet and triplet states for n = 8 repeat unit. Furthermore, a considerable distance between the unpaired electrons with a pure diradical character disrupts the π-bond covalency and localizes the unpaired spins at the polymers ends. However, replacing the BBT acceptor with iso-BBT leads to a closed-shell configuration with a low-spin ground-state and a localized spin density on the polymer cores. This study shows the significance of the judicious choice of π-conjugated scaffold in generating low- (S = 0) and high-spin (S = 1) ground-state in the neutral form, by modulation of spin topology in extended π-conjugated D-A polymers for emergent optoelectronic applications.

Benzobisthiadiazole-based high-spin donor-acceptor conjugated polymers with localized spin distribution

ACS Fall 2021

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.