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Title: Improved synthesis and crystal structure of the flexible pillared layer porous coordination polymer: Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN)4]

Journal Article · · CrystEngComm
DOI:https://doi.org/10.1039/c3ce00017f· OSTI ID:1129495
 [1];  [2];  [3];  [4];  [1];  [1];  [1];  [3];  [5]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Material Measurement Lab.
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States). URS Corp., South Park, PA (United States)
  3. Univ. of Chicago, IL (United States). ChemMatCARS
  4. Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry
  5. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
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This paper reports our synthesis of flexible coordination polymer, Ni(L)[Ni(CN)4], (L = 1,2-bis(4-pyridyl)ethylene (nicknamed bpene)), and its structural characterization using synchrotron single crystal X-ray diffraction. The structure of the purplish crystals has been determined to be monoclinic, space group P21/m, a = 13.5941(12) Å, b = 14.3621(12) Å, c = 14.2561(12) Å, β = 96.141(2)°, V = 2767.4(4) Å3, Z = 4, Dc = 1.46 g cm-1. Ni(bpene)[Ni(CN)4] assumes a pillared layer structure with layers defined by Ni[Ni(CN)4]n nets and bpene ligands acting as pillars. With the present crystallization technique which involves the use of concentrated ammonium hydroxide solution and dimethyl sulfoxide (DMSO), disordered free bpene ligands and solvents of crystallization (DMSO and water molecules) occupy the pores, resulting in a formula of Ni(bpene)[Ni(CN)4](1/2)bpene∙DMSO2H2O, or Ni2N7C24H25SO3. Without the inclusion of free bpene ligands and solvent molecules, the free volume is approximately 61% of the total volume; this free volume fraction is reduced to 50% with the free ligands present. Pores without the free ligands were found to have a local diameter of 5.7 Å and a main aperture of 3.5 Å. Based on the successful crystal synthesis, we also devised a new bulk synthetic technique which yielded a polycrystalline material with a significantly improved CO2 uptake as compared to the originally reported powder material. The improved synthetic technique yielded a polycrystalline material with 40% higher CO2 uptake compared to the previously reported powder material. An estimated 14.4 molecules of CO2 per unit cell was obtained.

Research Organization:
National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research
Sponsoring Organization:
USDOE Office of Fossil Energy (FE)
Grant/Contract Number:
FE0004000
OSTI ID:
1129495
Report Number(s):
A-CONTR-PUB-011; CRECF4
Journal Information:
CrystEngComm, Vol. 15, Issue 23; ISSN 1466-8033
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

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Cited By (5)

Powder X-ray structural studies and reference diffraction patterns for three forms of porous aluminum terephthalate, MIL-53(A1) journal June 2019
Topology of voids and channels in selected porphyrinic compounds journal September 2019
Bis(4-pyridyl)mercury – a new linear tecton in crystal engineering: coordination polymers and co-crystallization processes journal January 2015
Molecular simulation of capillary phase transitions in flexible porous materials journal March 2018
Structural Basis of CO2 Adsorption in a Flexible Metal-Organic Framework Material journal March 2019

Linked Research (1)

Figures / Tables (4)

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Related Subjects

36 MATERIALS SCIENCE
pillar layered solids
flexible metal organic framework
structurally dynamic
flexible porous coordination polymer
CO2 capture
spin crossover
Hofmann compound
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