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Title: Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs

Abstract

Here, metal–organic frameworks (MOFs) provide highly designable platforms to construct complex coordination architectures for targeted applications. Herein, we demonstrate that trans-coordinated metal centers with exposed equatorial positions can be placed in a MOF matrix. A Zr-based MOF, namely, PCN-160, was initially synthesized as a scaffold structure. Postsynthetic linker labilization was subsequently implemented to partially remove the original dicarboxylate linkers and incorporate pyridinecarboxylates. A pair of neighboring pyridyl groups was arranged at proper proximity within the framework to form trans-binding sites that accommodate different metal cations including Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+, and Pd 2+. Furthermore, the trans-coordinated Ni 2+ sites in porous frameworks can be readily accessed by substrates along the equatorial plane, facilitating the catalysis as manifested by the superior activity in ethylene dimerization over that observed for a cis-chelated catalyst.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [4];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [5];  [5]; ORCiD logo [2]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States)
  2. China Univ. of Petroleum (East China), Shandong (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Texas A&M Univ. at Qatar, Doha (Qatar)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1475583
Grant/Contract Number:  
A-0030; IIP-1632486; SC0001015; DGE-1252521; NPRP9-377-1-080; FE0026472
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 34; 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

Yuan, Shuai, Zhang, Peng, Zhang, Liangliang, Garcia-Esparza, Angel T., Sokaras, Dimosthenis, Qin, Jun -Sheng, Feng, Liang, Day, Gregory S., Chen, Wenmiao, Drake, Hannah F., Elumalai, Palani, Madrahimov, Sherzod T., Sun, Daofeng, and Zhou, Hong -Cai. Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs. United States: N. p., 2018. Web. doi:10.1021/jacs.8b04886.
Yuan, Shuai, Zhang, Peng, Zhang, Liangliang, Garcia-Esparza, Angel T., Sokaras, Dimosthenis, Qin, Jun -Sheng, Feng, Liang, Day, Gregory S., Chen, Wenmiao, Drake, Hannah F., Elumalai, Palani, Madrahimov, Sherzod T., Sun, Daofeng, & Zhou, Hong -Cai. Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs. United States. doi:10.1021/jacs.8b04886.
Yuan, Shuai, Zhang, Peng, Zhang, Liangliang, Garcia-Esparza, Angel T., Sokaras, Dimosthenis, Qin, Jun -Sheng, Feng, Liang, Day, Gregory S., Chen, Wenmiao, Drake, Hannah F., Elumalai, Palani, Madrahimov, Sherzod T., Sun, Daofeng, and Zhou, Hong -Cai. Wed . "Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs". United States. doi:10.1021/jacs.8b04886. https://www.osti.gov/servlets/purl/1475583.
@article{osti_1475583,
title = {Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs},
author = {Yuan, Shuai and Zhang, Peng and Zhang, Liangliang and Garcia-Esparza, Angel T. and Sokaras, Dimosthenis and Qin, Jun -Sheng and Feng, Liang and Day, Gregory S. and Chen, Wenmiao and Drake, Hannah F. and Elumalai, Palani and Madrahimov, Sherzod T. and Sun, Daofeng and Zhou, Hong -Cai},
abstractNote = {Here, metal–organic frameworks (MOFs) provide highly designable platforms to construct complex coordination architectures for targeted applications. Herein, we demonstrate that trans-coordinated metal centers with exposed equatorial positions can be placed in a MOF matrix. A Zr-based MOF, namely, PCN-160, was initially synthesized as a scaffold structure. Postsynthetic linker labilization was subsequently implemented to partially remove the original dicarboxylate linkers and incorporate pyridinecarboxylates. A pair of neighboring pyridyl groups was arranged at proper proximity within the framework to form trans-binding sites that accommodate different metal cations including Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Pd2+. Furthermore, the trans-coordinated Ni2+ sites in porous frameworks can be readily accessed by substrates along the equatorial plane, facilitating the catalysis as manifested by the superior activity in ethylene dimerization over that observed for a cis-chelated catalyst.},
doi = {10.1021/jacs.8b04886},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 34,
volume = 140,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

CCDC 1841688: Experimental Crystal Structure Determination
dataset, June 2018


CCDC 1841689: Experimental Crystal Structure Determination
dataset, June 2018


CCDC 1841691: Experimental Crystal Structure Determination: FINXUY : diaqua-dihydroxy-bis(pyridine-4-carboxylic acid)-copper
dataset, May 2018


CCDC 1841693: Experimental Crystal Structure Determination: FIPHIY : diaqua-bis(hydroxy)-bis(pyridine-4-carboxylic acid)-nickel
dataset, May 2018