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Issue 43, 2020
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Acyclic diaminocarbene-based Thiele, Chichibabin, and Müller hydrocarbons

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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.

Graphical abstract: Acyclic diaminocarbene-based Thiele, Chichibabin, and Müller hydrocarbons

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Article information


Submitted
01 Jul 2020
Accepted
01 Oct 2020
First published
02 Oct 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 11827-11833
Article type
Edge Article

Acyclic diaminocarbene-based Thiele, Chichibabin, and Müller hydrocarbons

A. Maiti, S. Chandra, B. Sarkar and A. Jana, Chem. Sci., 2020, 11, 11827
DOI: 10.1039/D0SC03622F

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