Homologous Critical Behavior in the Molecular Frameworks Zn(CN)2 and Cd(imidazolate)2 | Zendy

Ines E. Collings | Zendy; Andrew B. Cairns | Zendy; Amber L. Thompson | Zendy; Julia E. Parker | Zendy; Chiu C. Tang | Zendy; Matthew G. Tucker | Zendy; Jadna Catafesta | Zendy; Claire Levelut | Zendy; Julien Haines | Zendy; Vladimir Dmitriev | Zendy; Philip Pattison | Zendy; Andrew L. Goodwin | Zendy

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Homologous Critical Behavior in the Molecular Frameworks Zn(CN)₂ and Cd(imidazolate)₂

Author(s) -

Ines E. Collings,

Andrew B. Cairns,

Amber L. Thompson,

Julia E. Parker,

Chiu C. Tang,

Matthew G. Tucker,

Jadna Catafesta,

Claire Levelut,

Julien Haines,

Vladimir Dmitriev,

Philip Pattison,

Andrew L. Goodwin

Publication year - 2013

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/ja401268g

Subject(s) - chemistry , orthorhombic crystal system , imidazolate , crystallography , zeolitic imidazolate framework , zinc , hydrostatic pressure , tetrahedron , cyanide , phase transition , topology (electrical circuits) , molecular dynamics , crystal structure , inorganic chemistry , thermodynamics , computational chemistry , metal organic framework , adsorption , physics , mathematics , organic chemistry , combinatorics

Using a combination of single-crystal and powder X-ray diffraction measurements, we study temperature- and pressure-driven structural distortions in zinc(II) cyanide (Zn(CN)2) and cadmium(II) imidazolate (Cd(im)2), two molecular frameworks with the anticuprite topology. Under a hydrostatic pressure of 1.52 GPa, Zn(CN)2 undergoes a first-order displacive phase transition to an orthorhombic phase, with the corresponding atomic displacements characterized by correlated collective tilts of pairs of Zn-centered tetrahedra. This displacement pattern sheds light on the mechanism of negative thermal expansion in ambient-pressure Zn(CN)2. We find that the fundamental mechanical response exhibited by Zn(CN)2 is mirrored in the temperature-dependent behavior of Cd(im)2. Our results suggest that the thermodynamics of molecular frameworks may be governed by considerations of packing efficiency while also depending on dynamic instabilities of the underlying framework topology.

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