Affiliation:
1. Centre of Molecular and Macromolecular Studies Polish Academy of Sciences Sienkiewicza 112 90-363 Łódź Poland
2. Faculty of Chemistry University of Łódź Tamka 12 91-403 Łódź Poland
3. Department of Chemistry Middle Tennessee State University Murfreesboro TN-37132 USA
Abstract
AbstractReactions of a benzo[e][1,2,4]triazine with dilithiobenzenes lead to di‐Blatter diradicals connected at the N(1) positions via a spin coupling unit, 1,4‐phenylene or 1,3‐phenylene. Electrochemical analysis in MeCN revealed four one‐electron redox processes separated by 0.1–0.3 V in both diradicals. Variable temperature EPR measurements in polystyrene (PS) solid solutions gave the singlet‐triplet energy gaps ΔES‐T=2 J of −3.02(11) and −0.16(1) kcal mol−1 for 1,4‐phenylene and 1,3‐phenylene derivatives, respectively. The latter negative value was attributed to conformational properties of the diradical in the PS solid solution. Results suggest a simple and efficient access to a family of stable Blatter diradicals with a controllable S−T gap through a judicious choice of the arylene coupling unit. DFT calculations indicate that the triplet state is stabilized by (het)arylenes with low LUMO.
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
2 articles.
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