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

doi:10.1002/anie.202311044

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 af dette arbejde

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

7 Citationer (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.

Originalsprog	Engelsk
Artikelnummer	e202311044
Tidsskrift	Angewandte Chemie - International Edition
Vol/bind	62
Nummer	45
Antal sider	6
ISSN	1433-7851
DOI	https://doi.org/10.1002/anie.202311044
Status	Udgivet - nov. 2023

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Thomas, S. P., Singh, A., Grosjean, A., Alhameedi, K., Grønbech, T. B. E., Piltz, R., Edwards, A. J., & Iversen, B. B. (2023). The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides: Chalcogen Bonds versus Dynamic Se−Se/Te−Te Bonds. Angewandte Chemie - International Edition, 62(45), Artikel e202311044. https://doi.org/10.1002/anie.202311044

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

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.",

keywords = "Chalcogen Bond, Dynamic Bonds, Molecular Crystal, Structure-Property Relation, Thermochromism",

author = "Thomas, {Sajesh P.} and Ashi Singh and Arnaud Grosjean and Khidhir Alhameedi and Gr{\o}nbech, {Thomas Bj{\o}rn E.} and Ross Piltz and Edwards, {Alison J.} and Iversen, {Bo B.}",

year = "2023",

month = nov,

doi = "10.1002/anie.202311044",

language = "English",

volume = "62",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "45",

}

The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides: Chalcogen Bonds versus Dynamic Se−Se/Te−Te Bonds. / Thomas, Sajesh P.; Singh, Ashi; Grosjean, Arnaud et al.
I: Angewandte Chemie - International Edition, Bind 62, Nr. 45, e202311044, 11.2023.

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

TY - JOUR

T1 - The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides

T2 - Chalcogen Bonds versus Dynamic Se−Se/Te−Te Bonds

AU - Thomas, Sajesh P.

AU - Singh, Ashi

AU - Grosjean, Arnaud

AU - Alhameedi, Khidhir

AU - Grønbech, Thomas Bjørn E.

AU - Piltz, Ross

AU - Edwards, Alison J.

AU - Iversen, Bo B.

PY - 2023/11

Y1 - 2023/11

N2 - 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.

AB - 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.

KW - Chalcogen Bond

KW - Dynamic Bonds

KW - Molecular Crystal

KW - Structure-Property Relation

KW - Thermochromism

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U2 - 10.1002/anie.202311044

DO - 10.1002/anie.202311044

M3 - Journal article

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AN - SCOPUS:85172482829

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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M1 - e202311044

ER -

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

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