Acyclic diaminocarbene-based Thiele, Chichibabin, and Müller hydrocarbons.

Chemical Science
Avijit MaitiAnukul Jana

Abstract

Thiele, Chichibabin and Müller hydrocarbons are considered as classical Kekulé diradicaloids. Herein we report the synthesis and characterization of acyclic diaminocarbene (ADC)-based Thiele, Chichibabin, and Müller hydrocarbons. The calculated singlet-triplet energy gaps are ΔES-T = -27.96, -3.70, -0.37 kcal mol-1, respectively, and gradually decrease with the increasing length of the π-conjugated spacer (p-phenylene vs. p,p'-biphenylene vs. p,p''-terphenylene) between the two ADC-scaffolds. In agreement with the calculations, we also experimentally observed the enhancement of paramagnetic diradical character as a function of the length of the π-conjugated spacer. ADC-based Thiele's hydrocarbon is EPR silent and exhibits very well resolved NMR spectra, whereas ADC-based Müller's hydrocarbon displays EPR signals and featureless NMR spectra at room temperature. The spacer also has a strong influence on the UV-Vis-NIR spectra of these compounds. Considering that our methodology is modular, these results provide a convenient platform for the synthesis of an electronically modified new class of carbon-centered Kekulé diradicaloids.

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Citations

Mar 3, 2021·Journal of the American Chemical Society·Avijit MaitiAnukul Jana
Dec 5, 2021·Nature Communications·Ying Kai LohSimon Aldridge

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Methods Mentioned

BETA
NMR

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