TY - JOUR
T1 - Design and synthesis of new stable fluorenyl-based radicals
AU - Tian, Yi
AU - Uchida, Kazuyuki
AU - Kurata, Hiroyuki
AU - Hirao, Yasukazu
AU - Nishiuchi, Tomohiko
AU - Kubo, Takashi
N1 - Publisher Copyright:
© 2014 American Chemical Society.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 2014/9/10
Y1 - 2014/9/10
N2 - Organic neutral radicals have long fascinated chemists with a fundamental understanding of structure-reactivity relationships in organic reactions and with applications as new functional materials. However, the elusive nature of these radicals makes the synthesis, isolation, and characterization very challenging. In this work, the synthesis of three long-lived, fluorenyl-based radicals are reported. The geometry and electronic structures of these radicals were systematically investigated with a combination of various experimental methods, besides density functional theory (DFT) calculations, which include X-ray crystallographic analysis, electron spin resonance (ESR), electron nuclear double resonance (ENDOR), cyclic voltammetry, and UV-vis-NIR measurements. Their half-life periods (τ1/2) in air-saturated solution under ambient conditions were also determined. Surprisingly, all three radicals showed remarkable stabilities: τ1/2 = 7, 3.5, and 43 days.
AB - Organic neutral radicals have long fascinated chemists with a fundamental understanding of structure-reactivity relationships in organic reactions and with applications as new functional materials. However, the elusive nature of these radicals makes the synthesis, isolation, and characterization very challenging. In this work, the synthesis of three long-lived, fluorenyl-based radicals are reported. The geometry and electronic structures of these radicals were systematically investigated with a combination of various experimental methods, besides density functional theory (DFT) calculations, which include X-ray crystallographic analysis, electron spin resonance (ESR), electron nuclear double resonance (ENDOR), cyclic voltammetry, and UV-vis-NIR measurements. Their half-life periods (τ1/2) in air-saturated solution under ambient conditions were also determined. Surprisingly, all three radicals showed remarkable stabilities: τ1/2 = 7, 3.5, and 43 days.
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U2 - 10.1021/ja507005c
DO - 10.1021/ja507005c
M3 - Article
AN - SCOPUS:84907652215
VL - 136
SP - 12784
EP - 12793
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 36
ER -