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2,6‐Bis(pyrazolyl)pyridine Functionalised with Two Nitronylnitroxide and Iminonitroxide Radicals
Author(s) -
Zoppellaro Giorgio,
Geies Ahmed,
Enkelmann Volker,
Baumgarten Martin
Publication year - 2004
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400013
Subject(s) - chemistry , pyridine , radical , electron paramagnetic resonance , supramolecular chemistry , conjugated system , molecule , triplet state , photochemistry , crystallography , medicinal chemistry , nuclear magnetic resonance , organic chemistry , polymer , physics
During the last two decades, growing interest in the field of material chemistry has been focused on the synthetic design of organic high‐spin molecules for use as novel magnetic materials. Conjugated radicals based on the bis(pyrazolyl)pyridine core are very attractive in principle, since they per se combine optical, chelating and magnetic properties on a single molecular entity. The functionalisation of this core via the bis(4′‐formyl) derivatives with Ullman radicals results in novel functional biradicals, which may further be used for supramolecular architectures. In this paper we describe the synthesis, structure and properties of 2,6‐bis[4′‐(3‐oxo‐1‐oxyl‐4,4,5,5‐tetramethylimidazolin‐2‐yl)pyrazol‐1′‐yl]pyridine (Pz 2 PyNN) and 2,6‐bis[4‐(1‐oxyl‐4,4,5,5‐tetramethylimidazolin‐2‐yl)pyrazolyl]pyridine (Pz 2 PyIN). The two biradicals can clearly be differentiated by UV/Vis, IR and EPR spectroscopy. The optical absorptions of the blue Pz 2 PyNN appear around λ max = 610 nm (ϵ ≈ 1700 M −1 cm −1 ) while for Pz 2 PyIN the orange‐red colour arises from absorptions at λ max = 468 nm (ϵ ≈ 1400 M −1 cm −1 ) . A triplet ground state for the bis(nitronylnitroxide) Pz 2 PyNN with Δ E S‐T ≈ 11.8 ± 4.8 cm −1 can be deduced from the EPR studies because of the increase of the double integrated intensity times temperature at very low temperatures, indicating complete population of the triplet state. For the related bis(iminonitroxide) Pz 2 PyIN a much smaller (at least one order of magnitude lower) singlet−triplet energy gap with an upper limit of 0.7 cm −1 has been derived (0.7 ⪖ Δ E S‐T ⪖ −0.07 cm −1 ). The new multifunctional biradicals represent the first example of high‐spin molecules in the bis(pyrazolyl)pyridine family. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)