Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Mixed Phenyl and Thiophene Oligomers for Bridging Nitronyl Nitroxides

Mixed Phenyl and Thiophene Oligomers for Bridging Nitronyl Nitroxides
Prince Ravat, Victor I. Ovcharenko, Kubandiran Kolanji, Martin Baumgarten, Dieter Schollmeyer, Artem S. Bogomyakov
The synthesis of four nitronyl nitroxide (NN) biradicals is described which are conjugatively linked through p-ter-phenyl (PPP), ter-thiophene (TTT) and alternating phenylene (P) and thiophene (T) units as PTP and TPT. We first utilized Suzuki and Stille coupling reactions through protection and deprotection protocols to synthesize these (NN) biradicals. Single crystals were efficiently grown for radical precursors of 3, 5, 6, PPP-NNSi, PTP-NNSi, and final biradicals of TTT-NN, TPT-NN, and PPP-NN, whose structures and molecular packing were examined by X-ray diffraction studies. As a result, much smaller torsions between the NN and thiophene units (∼10°) in TTT-NN and TPT-NN than for NN and phenyl units (∼29°) in PPP-NN were observed due to smaller hindrance for a five vs a six membered ring. All four biradicals TTT-NN, TPT-NN, PTP-NN, and PPP-NN were investigated by EPR and optical spectroscopy combined with DFT calculations. The magnetic susceptibility was studied by SQUID measurements for TTT-NN and TPT-NN. The intramolecular exchange interactions for TPT-NN and TTT-NN were found in good agreement with the ones calculated by broken symmetry DFT calculations.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00435

DOI: 10.1021/acs.joc.7b00435

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