Abstract-Discovering connections between Terahertz vibrations and elasticity underpinning the collective dynamics of the HKUST-1 metal-organic framework

Matthew R Ryder,   B. Civalleri,   Gianfelice Cinque and  Jin-Chong Tan  

CrystEngComm, 2016, Accepted Manuscript

DOI: 10.1039/C5CE02347E
Received 01 Dec 2015, Accepted 21 Jan 2016
First published online 22 Jan 2016

http://pubs.rsc.org/en/Content/ArticleLanding/2016/CE/C5CE02347E?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FCE+(RSC+-+CrystEngComm+latest+articles)#!divAbstract

We employed a combination of theoretical and experimental techniques to study the metal-organic framework (MOF)-mechanics central to the paddle-wheel Cu₃(BTC)₂ porous structure, commonly designated as HKUST-1. Lattice dynamics of the hybrid framework at below 18 THz were measured by means of Raman and synchrotron far-infrared spectroscopy, and systematically correlated to collective vibrational modes computed from ab initio density functional theory (DFT). We have identified a number of intriguing low-energy framework vibration mechanisms, reminiscent of the ‘trampoline-like’ deformations and new oscillatory motions associated with Cu paddle-wheel ‘molecular rotors’. The three independent single-crystal elastic constants of the HKUST-1 (i.e. C₁₁, C₁₂ and C₄₄) were calculated using the DFT approach, taking into account the effects of dispersion corrections. We established the full elasticity solutions accompanying detailed deformation mechanisms that control its anisotropic mechanical properties, ranging from the Young’s and shear moduli to linear compressibility and Poisson’s ratio. Our results support the notion that the co-existance of soft modes and intrinsic shear distortions connected to the THz lattice dynamics dictate anomalous elastic phenomena, for exemplar: negative Poisson’s ratio (auxeticity), negative thermal expansion (NTE), and exceedingly low shear moduli property.