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Title: Pyridine-2,6-diyl dinitroxides as room-temperature triplet ligands

We have proposed tert-butyl 2-pyridyl nitroxide radicals as a promising paramagnetic chelating ligand, where the direct radical-metal bond leads to strong magnetic interaction. We successfully synthesized and isolated PyBN derivatives (pyridine-2,6-diyl bis(tert-butyl nitroxides)). The molecular and crystal structures of the target biradicals, MesPyBN, AntPyBN and tBuOPyBN were determined from the X-ray crystal structure analysis, which possess mesityl, 9-anthryl and tert-butoxy groups at the 5-position of the pyridine ring, respectively. The ground triplet state was characterized by means of SQUID susceptometry for each compound. On heating, the χ{sub m}T values of all the PyBN derivatives increased and reached a plateau at ca. 1.0 cm{sup 3} K mol{sup −1} at 300 K. It implies that biradicals behaved as triplet molecules even at room temperature, or 2J/k{sub B} >> 300 K. From the decay monitored in solution electron-spin resonance spectroscopy, MesPyBN was the most persistent, while tBuOPyBN was the most reactive, of the three.
Authors:
; ;  [1]
  1. Department of Engineering Science, The University of Electro-Communications, Tokyo (Japan)
Publication Date:
OSTI Identifier:
22494590
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Conference Proceedings; Journal Volume: 1709; Journal Issue: 1; Conference: IRAGO conference 2015: 360 degree outlook on critical scientific and technological challenges for a sustainable society, Aichi (Japan), 22-23 Oct 2015; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; CHELATING AGENTS; CRYSTAL STRUCTURE; ELECTRON SPIN RESONANCE; LIGANDS; MOLECULES; PARAMAGNETISM; PYRIDINE; RADICALS; SPECTROSCOPY; SQUID DEVICES; TEMPERATURE RANGE 0273-0400 K; TRIPLETS; X RADIATION