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A Dynamic Triradical: Synthesis, Crystal Structure, and Spin Frustration

Xue Dong, Qian‐Cheng Luo, Yu Zhao, Tao Wang, Quanchun Sun, Runbo Pei, Yue Zhao, Yan‐Zhen Zheng, Xinping Wang

2023Journal of the American Chemical Society25 citationsDOI

Abstract

Polyradicals, i.e., multispin organic molecules, are playing important roles in radical-based material applications for their spin-spin interaction. A dynamic covalently bonded multispin molecule may endow materials with added function such as memory and switching. However, such a species has yet to be reported. We here report the synthesis, characterization, and crystal structure of a dynamic triradical species. It is generated by the self-assembly of two molecules through a Lewis acid coupled electron transfer. The crystalline species is spin-frustrated without Jahn-Teller distortion at low temperature, while it dissociates back to diamagnetic starting material in solution at high temperature. The reversible process is tracked by variable-temperature NMR, EPR, and UV-vis-NIR spectroscopy. Isolation, property study, and dynamic bonding investigation on such a species lay the foundation for the design of functional polyradicals with potential application as memory or switching devices.

Topics & Concepts

ChemistryFrustrationElectron paramagnetic resonanceMoleculeDiamagnetismSpin (aerodynamics)Covalent bondChemical physicsCrystal structureCrystallographyCondensed matter physicsNuclear magnetic resonanceOrganic chemistryMagnetic fieldPhysicsEngineeringQuantum mechanicsAerospace engineeringMagnetism in coordination complexesOrganic and Molecular Conductors ResearchMetal-Organic Frameworks: Synthesis and Applications