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Grosjean, Arnaud
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Topics
Publications (6/6 displayed)
- 2023The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides: Chalcogen Bonds versus Dynamic Se−Se/Te−Te Bondscitations
- 2023Coordination Sphere Flexibility Leads to Elastic Deformation in a One-Dimensional Coordination Polymer Crystalcitations
- 2023The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides:Chalcogen Bonds versus Dynamic Se−Se/Te−Te Bondscitations
- 2018Crystallinity and microstructural versatility in the spin-crossover polymeric material [Fe(Htrz)2(trz)](BF4)citations
- 2011The 1-D polymeric structure of the [Fe(NH2trz)3](NO3)2*nH2O (with n = 2) spin crossover compound proven by single crystal investigationscitations
- 2009Tape casting of proton conducting ceramic materialcitations
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article
The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides: Chalcogen Bonds versus Dynamic Se−Se/Te−Te Bonds
Abstract
e 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.