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À propos de : Probing Electronic Communication in Stable Benzene-BridgedVerdazyl Diradicals        

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  • Probing Electronic Communication in Stable Benzene-BridgedVerdazyl Diradicals
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  • Two benzene-bridged N,N‘-bis(isopropyl)6-oxoverdazyl diradicals 7a (1,4-benzene-bridged) and 7b (1,3-benzene-bridged) were prepared and studied by an array of physicochemical techniques aimed at elucidatingthe intramolecular electronic and magnetic coupling between verdazyl chromophores. The very highstability of these diradicals permits comprehensive investigations of their properties for the first time.The UV−vis spectra suggest negligible direct conjugative overlap involving the radical SOMOs, althoughsignificant differences in higher energy absorptions suggest that radical orbitals other than the SOMOare likely communicating via the central p-phenylene bridge in 7a. The electrochemical features of thetwo diradicals are nearly identical; in each derivative, both radicals are oxidized essentially independentlywhile the reductions occur in a stepwise manner with differences of ∼100mV between the two reductions.EPR and magnetic susceptibility collectively indicate that the para-bridged diradical is weaklyantiferromagnetically coupled while the meta analogue is weakly ferromagnetically coupled, in accordwith the topology of the substitution pattern on the central benzene ring.
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