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High-spin ground-state organic materials with unique spin topology can significantly impact molecular magnetism, spintronics, and quantum computing devices. However, strategies to control the spin topology and alignment of the unpaired spins in different molecular orbitals are not well understood. Here, we report modulating spin distribution along the molecular backbone in high-spin ground-state donor–acceptor (D–A) conjugated polymers. Density functional theory calculations indicate that substitution of different heteroatoms (such as C, Si, N, and Se) alters the aromatic character in the thiadiazole unit of the benzobisthiadiazole (BBT) acceptor and modulates the oligomer length to result in high-spin triplet ground-state, orbital and spin topology. The C, Si, and Se atom substituted polymers show a localized spin density at the two opposite ends of the polymers. However, a delocalized spin distribution is observed in the N substituted polymer. We find that the hybridization (sp 3 vs. sp 2 ) of the substituent atom plays an important role in controlling the electronic structure of these materials. This study shows that atomistic engineering is an efficient technique to tune the spin topologies and electronic configurations in the high-spin ground-state donor–acceptor conjugated polymers, compelling synthetic targets for room-temperature magnetic materials.
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Benzobisthiadiazole-based high-spin donor–acceptor conjugated polymers with localized spin distribution
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 degenerate singlet and triplet states for a 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 polymer 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 scaffolds in generating low- ( S = 0) and high-spin ( S = 1) ground-states in the neutral form, by modulation of spin topology in extended π-conjugated D–A polymers for emergent optoelectronic applications.
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- Award ID(s):
- 1757220
- PAR ID:
- 10251852
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 2
- Issue:
- 9
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 2943 to 2955
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1MA00144B
