The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides: Chalcogen Bonds versus Dynamic Se−Se/Te−Te Bonds

Sajesh P. Thomas*, Ashi Singh, Arnaud Grosjean, Khidhir Alhameedi, Thomas Bjørn E. Grønbech, Ross Piltz, Alison J. Edwards, Bo B. Iversen*

*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

7 Citations (Scopus)

Abstract

We report thermochromism in crystals of diphenyl diselenide (dpdSe) and diphenyl ditelluride (dpdTe), which is at variance with the commonly known mechanisms of thermochromism in molecular crystals. Variable temperature neutron diffraction studies indicated no conformational change, tautomerization or phase transition between 100 K and 295 K. High-pressure crystallography studies indicated no associated piezochromism in dpdSe and dpdTe crystals. The evolution of the crystal structures and their electronic band structure with pressure and temperature reveal the contributions of intramolecular and intermolecular factors towards the origin of thermochromism—especially the intermolecular Se⋅⋅⋅Se and Te⋅⋅⋅Te chalcogen bonds and torsional modes of vibrations around the dynamic Se−Se and Te−Te bonds. Further, a co-crystal of dpdSe with iodine (dpdSe-I2) and an alloy crystal of dpdSe and dpdTe implied a predominantly intramolecular origin of the observed thermochromism associated with vibronic coupling.

Original languageEnglish
Article numbere202311044
JournalAngewandte Chemie - International Edition
Volume62
Issue45
Number of pages6
ISSN1433-7851
DOIs
Publication statusPublished - Nov 2023

Keywords

  • Chalcogen Bond
  • Dynamic Bonds
  • Molecular Crystal
  • Structure-Property Relation
  • Thermochromism

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