Both dipyrromethene complexes and radicals of heavier main group elements have been of high interest. However, cationic germanium radicals and dipyrromethene-based radicals of heavier main group elements are still escaped to be isolated. Herein, we report the isolation and full characterization of a neutral Ge(I)-masked dipyrromethene-based radical 3 and the first cationic Ge(III)-centered radical 5•+ as stable crystalline solids. 3 behaves as a germanium(I) radical in its reaction with diphenyl disulfide to form the Ge-S bond, although X-ray crystallographic, EPR spectroscopic, computational studies revealed that the unpaired electron of 3 is mainly delocalized over the C 9 N 2 Ge backbone and the allylic radical character is also significant in 3. In contrast to 3, the spin density of 5•+ is mainly localized at the Ge center with minor contribution from the dipyrromethene ligand. Moreover, reduction of 5•+ with potassium graphite quantitatively regenerates 5, illustrating a reversible one-electron redox pair.
Herein, we report the isolation of bis-BN-based species 1 and 2 with multiple stable redox states. Their ground states are tunable with 1 as a closed-shell singlet and 2 as an open-shell singlet with a small singlet-triplet gap.
Two radical cations of bis-BN-based analogues of Thiele’s hydrocarbons were facilely synthesized, fully characterized, and theoretically investigated. One-electron oxidation leads to the reduced bond length alternation and NICS values of...
Boron-dipyrromethene (BODIPY) compounds have been the subject of intense scrutiny over the past decades owing to their unique properties and various applications; however, structurally characterized BODIPY-centered radicals are still limited...
Comprehensive SummaryMüller's hydrocarbon and its analogues, classical examples of Kekulé diradicaloids, have gained great attention. However, because of their highly reactivities, their isolation and structural characterizations are still challenging. Herein, we report the isolation of two bis‐BN‐based analogues of Müller's hydrocarbon (1 and 2) as crystalline solids in moderate yields. Experimental results and theoretical studies demonstrated that compound 1 possessing the terminal 1,3,2‐diazaboryl groups is an open‐shell singlet diradicaloid, which is contrast to the closed‐shell singlet ground states of the bis‐BN‐based analogues of Thiele's and Chichibabin's hydrocarbon with the same terminal boryl groups, illustrating the strong influence of the central linkers on the ground state. Additionally, replacement of the terminal 1,3,2‐diazaboryl groups in 1 with the bis(2,4,6‐triisopropylphenyl)boryl groups affords 2 with higher diradical character and a smaller singlet‐triplet energy gap.This article is protected by copyright. All rights reserved.
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