A Stable Triplet‐Ground‐State Conjugated Diradical Based on a Diindenopyrazine Skeleton. Issue 9 (18th January 2021)

• Record Type: Journal Article
• Authors: Wang, Zi‐Yuan; Dai, Ya‐Zhong; Ding, Li; Dong, Bo‐Wei; Jiang, Shang‐Da; Wang, Jie‐Yu; Pei, Jian
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 9(2021)
• Page Start: 4594
• Page End: 4598
• Publication Date: 2021-01-18
• Subjects: conjugated radicals -- high-spin -- pyrazine -- singlet–triplet gap -- stable radicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202012989
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: High‐spin conjugated radicals have great potential in magnetic materials and organic spintronics. However, to obtain high‐spin conjugated radicals is still quite challenging due to their poor stability. We report the successful synthesis and isolation of a stable triplet conjugated diradical, 10, 12‐diaryldiindeno[1, 2‐ b :2′, 1′‐ e ]pyrazine ( m ‐DIP ). With the m ‐xylylene analogue skeleton containing electron‐deficient sp 2 ‐nitrogen atoms, m ‐DIP displays significant aromatic character within its pyrazine ring and its spin density mainly delocalizes on the meta ‐pyrazine unit, making it a triplet ground state conjugated diradical. Our work provides an effective "spin density tuning" strategy for stable high‐spin conjugated radicals. Abstract : A stable triplet‐ground‐state conjugated diradical with pyrazine as a linker group was synthesized with a half‐life time of about 22 days under ambient conditions. The electron‐deficient pyrazine unit impedes spin delocalization to the peripheral phenyl rings, which increases the spin density distribution on the central meta ‐pyrazine unit, leading to a large Δ E S‐T .