Angeloski Alexander, Galaviz Pablo, Mole Richard A, Piltz Ross O, McDonagh Andrew M, Ennis Courtney, Appadoo Dominique
Australian Nuclear Science Technology Organisation, Lucas Heights, New South Wales 2234, Australia.
School of Mathematical and Physical Sciences, University of Technology Sydney, Ultimo, New South Wales 2007, Australia.
J Am Chem Soc. 2025 Mar 5;147(9):8032-8047. doi: 10.1021/jacs.5c01140. Epub 2025 Feb 20.
The thermosalient transformation in nickel(II) bis(diisopropyl)dithiocarbamate has been investigated using selective deuteration. The deuterated crystals undergo a reversible displacive phase transition that is ∼4 K higher in temperature compared to the protonated analogue. Neutron, synchrotron, density-functional theory, and calorimetric techniques were utilized to demonstrate the substantial effect of deuterium. All techniques demonstrated the equivalence of the mechanism on an atomic scale between the protonated and deuterated complexes. The data collected in this study reveal details of the changes of atomic motion that underpin the thermosalience inherent in this system. Deuterium decreased the frequency of atomic vibrations thus increasing the temperature of the observed transformation. This study represents a key advancement in the field of thermosalient molecular systems and provides insights into the control and manipulation of thermosalient materials.
利用选择性氘化研究了二（二异丙基）二硫代氨基甲酸镍（II）中的热致突出转变。氘化晶体经历了一个可逆的位移相变，其温度比质子化类似物高约4K。利用中子、同步加速器、密度泛函理论和量热技术来证明氘的显著影响。所有技术都证明了质子化和氘化配合物在原子尺度上机制的等效性。本研究收集的数据揭示了原子运动变化的细节，这些变化是该系统固有热致突出的基础。氘降低了原子振动的频率，从而提高了观察到的转变温度。这项研究代表了热致突出分子系统领域的一项关键进展，并为热致突出材料的控制和操纵提供了见解。
