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 for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-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 language	English
Article number	e202311044
Journal	Angewandte Chemie - International Edition
Volume	62
Issue	45
Number of pages	6
ISSN	1433-7851
DOIs	https://doi.org/10.1002/anie.202311044
Publication status	Published - Nov 2023

Keywords

Chalcogen Bond
Dynamic Bonds
Molecular Crystal
Structure-Property Relation
Thermochromism

Access to Document

10.1002/anie.202311044

Cite this

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), Article e202311044. https://doi.org/10.1002/anie.202311044

@article{c92cf4f8ccf4415bab13c875480bfd6d,

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.
In: Angewandte Chemie - International Edition, Vol. 62, No. 45, e202311044, 11.2023.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › 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

UR - http://www.scopus.com/inward/record.url?scp=85172482829&partnerID=8YFLogxK

U2 - 10.1002/anie.202311044

DO - 10.1002/anie.202311044

M3 - Journal article

C2 - 37718313

AN - SCOPUS:85172482829

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 45

M1 - e202311044

ER -

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

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this