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Crystallography of Representative MOFs Based on Pillared Cyanonickelate (PICNIC) Architecture

Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA
National Energy Technology Laboratory, United States Department of Energy, P.O. Box 10940, Pittsburgh, PA 15236, USA
AECOM, South Park, PA 15219, USA
ChemMatCARS, University of Chicago, Argonne, IL 60439, USA
Author to whom correspondence should be addressed.
Academic Editor: Helmut Cölfen
Crystals 2016, 6(9), 108;
Received: 2 July 2016 / Revised: 18 August 2016 / Accepted: 22 August 2016 / Published: 5 September 2016
PDF [4164 KB, uploaded 7 September 2016]


The pillared layer motif is a commonly used route to porous coordination polymers or metal organic frameworks (MOFs). Materials based on the pillared cyano-bridged architecture, [Ni’(L)Ni(CN)4]n (L = pillar organic ligands), also known as PICNICs, have been shown to be especially diverse where pore size and pore functionality can be varied by the choice of pillar organic ligand. In addition, a number of PICNICs form soft porous structures that show reversible structure transitions during the adsorption and desorption of guests. The structural flexibility in these materials can be affected by relatively minor differences in ligand design, and the physical driving force for variations in host-guest behavior in these materials is still not known. One key to understanding this diversity is a detailed investigation of the crystal structures of both rigid and flexible PICNIC derivatives. This article gives a brief review of flexible MOFs. It also reports the crystal structures of five PICNICS from our laboratories including three 3-D porous frameworks (Ni-Bpene, NI-BpyMe, Ni-BpyNH2), one 2-D layer (Ni-Bpy), and one 1-D chain (Ni-Naph) compound. The sorption data of BpyMe for CO2, CH4 and N2 is described. The important role of NH3 (from the solvent of crystallization) as blocking ligands which prevent the polymerization of the 1-D chains and 2-D layers to become 3D porous frameworks in the Ni-Bpy and Ni-Naph compounds is also addressed. View Full-Text
Keywords: MOFs; Flexible Ni(CN)4-based metal-organic frameworks; crystallography; structure and adsorption properties MOFs; Flexible Ni(CN)4-based metal-organic frameworks; crystallography; structure and adsorption properties

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Wong-Ng, W.; Culp, J.T.; Chen, Y.-S. Crystallography of Representative MOFs Based on Pillared Cyanonickelate (PICNIC) Architecture. Crystals 2016, 6, 108.

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