Deuterium Perturbs the Molecular Arrangement in the Solid State

Abstract

KEYWORDS: hydrogen/deuterium exchange, isotope effect, isotopic polymorphism, influence on crystallization behavior ABSTRACT:Hydrogen/deuterium (H/D)-exchange, is generally seen as a negligible criterion in the formation of crystal structures of chemical compounds. On the other hand, it could already be shown that the aggregation of molecules in the solid state of selected organic and inorganic compounds can be very sensitive to the small H/D-change in the isotopic substitution pattern of the considered molecules or the use of deuterated solvents during the crystallisation process. This perspective highlights the extraordinary aggregation behavior in certain cases of deuterated versus the non-deuterated small inorganic and organic compounds.

Deuterium‐ and Tritium‐Labelled Compounds: Applications in the Life Sciences

“…[80] structure upon deuterium labelling have been reported. [100] Additionally,m olecular aggregation in the solid state can be sensitive to the use of deuterated solvents during the crystallization process. [101] In supramolecular systems,i sotope effects on binding affinities,w ith enhanced stabilities observed for deuterated guests in self-assembled capsules, [102] could be due to the reduced steric interactions arising from the shorter CÀD bonds rather than stronger more attractive CD-p interactions.…”

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

“…Could crystal structures of organic semiconductors be impacted? Although some exceptions exist, deuterium perturbs only slightly the molecular arrangement in the solid‐state . Rubrene 3 and its deuterated analog exhibit the same crystal structure and maintain its benchmark transport properties, with µ above 10 cm 2 V −1 s −1 at room temperature and µ = 45 cm 2 V −1 s −1 around 100 K .…”

The influence of deuteration on the crystal structure of hybrid halide perovskites: a temperature-dependent neutron diffraction study of FAPbBr3

“…Although it was assumed that the deuteration in most cases does not influence the crystal structure (Fisher & Helliwell, 2008), it has been reported by Shi et al (2018) and Whitfield et al (2016) that small changes in bond length and angles can occur. Merz & Kupka (2015) report on changes in the geometric arrangements of molecules in a crystal framework after the replacement of protium (H) by deuterium (D). Furthermore, Harwell et al (2018) report on changes in physical properties caused by deuteration of the FA molecule.…”