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Title: Crystalline Coordination Networks of Zero-Valent Metal Centers: Formation of a 3-Dimensional Ni(0) Framework with m-Terphenyl Diisocyanides

Abstract

A permanently porous, three-dimensional metal–organic material formed from zero-valent metal nodes is presented. Combination of ditopic m-terphenyl diisocyanide, [CNAr Mes2] 2, and the d 10 Ni(0) precursor Ni(COD) 2, produces a porous metal–organic material featuring tetrahedral [Ni(CNAr Mes2) 4] n structural sites. X-ray absorption spectroscopy provides firm evidence for the presence of Ni(0) centers, whereas gas-sorption and thermogravimetric analysis reveal the characteristics of a robust network with a microdomain N 2-adsorption profile.

Authors:
 [1];  [2];  [1];  [1];  [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (United States). Dept. of Chemistry and Biochemistry
  2. Cornell Univ., Ithaca, NY (United States). Baker Lab., Dept. of Chemistry and Chemical Biology
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1409488
Grant/Contract Number:
SC0008058; AC02-76SF00515
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 48; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Agnew, Douglas W., DiMucci, Ida M., Arroyave, Alejandra, Gembicky, Milan, Moore, Curtis E., MacMillan, Samantha N., Rheingold, Arnold L., Lancaster, Kyle M., and Figueroa, Joshua S.. Crystalline Coordination Networks of Zero-Valent Metal Centers: Formation of a 3-Dimensional Ni(0) Framework with m-Terphenyl Diisocyanides. United States: N. p., 2017. Web. doi:10.1021/jacs.7b09569.
Agnew, Douglas W., DiMucci, Ida M., Arroyave, Alejandra, Gembicky, Milan, Moore, Curtis E., MacMillan, Samantha N., Rheingold, Arnold L., Lancaster, Kyle M., & Figueroa, Joshua S.. Crystalline Coordination Networks of Zero-Valent Metal Centers: Formation of a 3-Dimensional Ni(0) Framework with m-Terphenyl Diisocyanides. United States. doi:10.1021/jacs.7b09569.
Agnew, Douglas W., DiMucci, Ida M., Arroyave, Alejandra, Gembicky, Milan, Moore, Curtis E., MacMillan, Samantha N., Rheingold, Arnold L., Lancaster, Kyle M., and Figueroa, Joshua S.. 2017. "Crystalline Coordination Networks of Zero-Valent Metal Centers: Formation of a 3-Dimensional Ni(0) Framework with m-Terphenyl Diisocyanides". United States. doi:10.1021/jacs.7b09569.
@article{osti_1409488,
title = {Crystalline Coordination Networks of Zero-Valent Metal Centers: Formation of a 3-Dimensional Ni(0) Framework with m-Terphenyl Diisocyanides},
author = {Agnew, Douglas W. and DiMucci, Ida M. and Arroyave, Alejandra and Gembicky, Milan and Moore, Curtis E. and MacMillan, Samantha N. and Rheingold, Arnold L. and Lancaster, Kyle M. and Figueroa, Joshua S.},
abstractNote = {A permanently porous, three-dimensional metal–organic material formed from zero-valent metal nodes is presented. Combination of ditopic m-terphenyl diisocyanide, [CNArMes2]2, and the d10 Ni(0) precursor Ni(COD)2, produces a porous metal–organic material featuring tetrahedral [Ni(CNArMes2)4]n structural sites. X-ray absorption spectroscopy provides firm evidence for the presence of Ni(0) centers, whereas gas-sorption and thermogravimetric analysis reveal the characteristics of a robust network with a microdomain N2-adsorption profile.},
doi = {10.1021/jacs.7b09569},
journal = {Journal of the American Chemical Society},
number = 48,
volume = 139,
place = {United States},
year = 2017,
month =
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/jacs.7b09569

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  • A permanently porous, three-dimensional metal–organic material formed from zero-valent metal nodes is presented. Combination of ditopic m-terphenyl diisocyanide, [CNAr Mes2] 2, and the d 10 Ni(0) precursor Ni(COD) 2, produces a porous metal–organic material featuring tetrahedral [Ni(CNAr Mes2) 4] n structural sites. X-ray absorption spectroscopy provides firm evidence for the presence of Ni(0) centers, whereas gas-sorption and thermogravimetric analysis reveal the characteristics of a robust network with a microdomain N 2-adsorption profile.
  • Here, the preparation of 3D and 2D Cu(I) coordination networks using ditopic m-terphenyl isocyanides is described. The incorporation of sterically encumbering substituents enables the controlled, solid-state preparation of Cu(I) tris-isocyanide nodes with a labile solvent ligand in a manner mirroring solution-phase chemistry of monomeric complexes. The protection afforded by the m-terphenyl groups is also shown to engender significant stability towards heat as well as acidic or basic conditions, resulting in robust single-metal-node networks that can transition from 3D to 2D extended structures.
    Cited by 1
  • Here, the preparation of 3D and 2D Cu(I) coordination networks using ditopic m-terphenyl isocyanides is described. The incorporation of sterically encumbering substituents enables the controlled, solid-state preparation of Cu(I) tris-isocyanide nodes with a labile solvent ligand in a manner mirroring solution-phase chemistry of monomeric complexes. The protection afforded by the m-terphenyl groups is also shown to engender significant stability towards heat as well as acidic or basic conditions, resulting in robust single-metal-node networks that can transition from 3D to 2D extended structures.
  • Four types of metal-organic structures exhibiting specific dimensionality were studied using scanning tunneling microscopy and Monte Carlo simulations. The four structures were self-assembled out of specifically designed molecular building blocks via the same coordination motif on an Au(111) surface. We found that the four structures behaved differently in response to thermal annealing treatments: The two-dimensional structure was under thermodynamic control while the structures of lower dimension were under kinetic control. Monte Carlo simulations revealed that the self-assembly pathways of the four structures are associated with the characteristic features of their specific heat. These findings provide insights into how the dimensionalitymore » of supramolecular coordination structures affects their thermodynamic properties.« less
  • Nickel, palladium, platinum, or silver were solvated in a suitable solvent at low temperature; alumina or silica was impregnated with the solution; and the solvent was desorbed. Electron microscopic and X-ray studies of the nickel-toluene catalysts showed Vertical Bar3; 40 A., crystallites for up to 9Vertical Bar3< loading, and up to 100 A. crystallites for up to 23Vertical Bar3< loading. Toluene hydrogenation to methylcyclohexane was optimum on a nickel-toluene-alumina catalyst containing approx. 0.4Vertical Bar3< nickel and pretreated under vacuum at 500/sup 0/C. A 6.8Vertical Bar3< nickel-toluene on alumina catalyst was more active for 1-butene hydrogenation to butane than the unsupportedmore » catalyst and was active in 1-butene isomerization in the presence of hydrogen, but unlike the unsupported catalyst, it did not catalyze the 1-butene isomerization in the absence of hydrogen. The hydrogenation of 1,3-butadiene proceeded on the 6.8Vertical Bar3< nickel-toluene on alumina catalyst in a manner similar to that on the unsupported catalyst.« less