2,7-Di-tert-butyl-9,9′(10H,10′H)-spirobiacridine-10,10′-dioxyl as a ground triplet biradical: The role of tert-butylation

被引：5

作者：

Ichihashi, Kana ^{[1
]}

Kanetomo, Takuya ^{[2
]}

Enomoto, Masaya ^{[2
]}

Ishida, Takayuki ^{[1
]}

机构：

[1] Univ Electrocommun, 1-5-1 Chofugaoka, Chofu, Tokyo 1828585, Japan

[2] Tokyo Univ Sci, Shinjuku Ku, 1-3 Kagurazaka, Tokyo 1628601, Japan

来源：

TETRAHEDRON LETTERS | 2020年 / 61卷 / 43期

关键词：

Spiro compound; Biradical; High-spin molecule; Intermolecular interaction; Aminoxyl; SPIN; NITROSODISULPHONATES; BISTABILITY; TRANSITION; CHARACTER; RESONANCE;

D O I：

10.1016/j.tetlet.2020.152428

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis of a doubly tert-butylated spirobiradical, 2,7-di-tert-butyl-9,9'(10H,10'H)-spirobiacridine-10,10'-dioxyl is reported. The X-ray diffraction study clarified that the two dihydroacridine skeletons were fused at the sp(3)-carbon atom affording a cruciform structure. The frozen-solution electron spin resonance spectrum showed a typical zero-field-splitting pattern. The magnetic study revealed the presence of an intramolecular ferromagnetic interaction with 2J/k(B) = +22.3(5) K. The density-functional-theory calculation results are entirely consistent with the experimental results. After comparison with the known unsubstituted spirobiradical, we can conclude that tert-butylation is a useful method to reduce the intermolecular interaction without breaking the degeneracy of the singly occupied molecular orbitals. (C) 2020 Elsevier Ltd. All rights reserved.

引用

页数：5