Issue 10, 2016

Thermally controlling the singlet–triplet energy gap of a diradical in the solid state

Abstract

Diradicals, molecules with two unpaired electrons, are reactive intermediates that play an important role in many fields. Their defining feature is the energy difference between their singlet and triplet states, which provides direct information on the extent of their electron exchange interactions. Such knowledge is essential for understanding their diradical character, which is controllable internally by modification of the electronic and steric properties of the substituents. We now report that the energy gap of a diradical in the solid state can also be controlled by an external stimulus. The dication diradical of 4,4′′-di(bisphenylamino)-p-terphenyl exhibits two singlet states with different exchange coupling constants at different temperatures as determined by SQUID and EPR measurements. The behavior is induced by the conformation change of the terphenyl bridge, the key structural unit of the species. The work presents an unprecedented instance of a thermally controllable singlet–triplet gap for a crystalline diradical and provides a novel diradical material relevant to the design of functional materials.

Graphical abstract: Thermally controlling the singlet–triplet energy gap of a diradical in the solid state

Supplementary files

Article information

Article type
Edge Article
Submitted
26 Apr. 2016
Accepted
28 Jūn. 2016
First published
28 Jūn. 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 6514-6518

Thermally controlling the singlet–triplet energy gap of a diradical in the solid state

Y. Su, X. Wang, L. Wang, Z. Zhang, X. Wang, Y. Song and P. P. Power, Chem. Sci., 2016, 7, 6514 DOI: 10.1039/C6SC01825D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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