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Title: Spectroscopic Evidence of Pore Geometry Effect on Axial Coordination of Guest Molecules in Metalloporphyrin-Based Metal Organic Frameworks

Abstract

A systematic comparison of host–guest interactions in two iron porphyrin-based metal–organic frameworks (MOFs), FeCl-PCN222 and FeCl-PCN224, with drastically different pore sizes and geometries is reported in this fundamental spectroscopy study. Guest molecules (acetone, imidazole, and piperidine) of different sizes, axial binding strengths, and reactivity with the iron porphyrin centers are employed to demonstrate the range of possible interactions that occur at the porphyrin sites inside the pores of the MOF. Binding patterns of these guest species under the constraints of the pore geometries in the two frameworks are established using multiple spectroscopy methods, including UV–vis diffuse reflectance, Raman, X-ray absorption, and X-ray emission spectroscopy. Line shape analysis applied to the latter method provides quantitative information on axial ligation through its spin state sensitivity. The observed coordination behaviors derived from the spectroscopic analyses of the two MOF systems are compared to those predicted using space-filling models and relevant iron porphyrin molecular analogues. While the space-filling models show the ideal axial coordination behavior associated with these systems, the spectroscopic results provide powerful insight into the actual binding interactions that occur in practice. Evidence for potential side reactions occurring within the pores that may be responsible for the observed deviation from model coordinationmore » behavior in one of the MOF/guest molecule combinations is presented and discussed in the context of literature precedent.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Rutgers Univ., Newark, NJ (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1431368
Grant/Contract Number:  
AC02-76SF00515; AC02-06CH11357; SC0012704; DMR-1455127; DMR-1332208
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 6; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
iron; pyrroles; metal organic frameworks; quantum mechanics; piperidines

Citation Formats

Kucheryavy, Pavel, Lahanas, Nicole, and Lockard, Jenny V. Spectroscopic Evidence of Pore Geometry Effect on Axial Coordination of Guest Molecules in Metalloporphyrin-Based Metal Organic Frameworks. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b00117.
Kucheryavy, Pavel, Lahanas, Nicole, & Lockard, Jenny V. Spectroscopic Evidence of Pore Geometry Effect on Axial Coordination of Guest Molecules in Metalloporphyrin-Based Metal Organic Frameworks. United States. doi:10.1021/acs.inorgchem.8b00117.
Kucheryavy, Pavel, Lahanas, Nicole, and Lockard, Jenny V. Thu . "Spectroscopic Evidence of Pore Geometry Effect on Axial Coordination of Guest Molecules in Metalloporphyrin-Based Metal Organic Frameworks". United States. doi:10.1021/acs.inorgchem.8b00117. https://www.osti.gov/servlets/purl/1431368.
@article{osti_1431368,
title = {Spectroscopic Evidence of Pore Geometry Effect on Axial Coordination of Guest Molecules in Metalloporphyrin-Based Metal Organic Frameworks},
author = {Kucheryavy, Pavel and Lahanas, Nicole and Lockard, Jenny V.},
abstractNote = {A systematic comparison of host–guest interactions in two iron porphyrin-based metal–organic frameworks (MOFs), FeCl-PCN222 and FeCl-PCN224, with drastically different pore sizes and geometries is reported in this fundamental spectroscopy study. Guest molecules (acetone, imidazole, and piperidine) of different sizes, axial binding strengths, and reactivity with the iron porphyrin centers are employed to demonstrate the range of possible interactions that occur at the porphyrin sites inside the pores of the MOF. Binding patterns of these guest species under the constraints of the pore geometries in the two frameworks are established using multiple spectroscopy methods, including UV–vis diffuse reflectance, Raman, X-ray absorption, and X-ray emission spectroscopy. Line shape analysis applied to the latter method provides quantitative information on axial ligation through its spin state sensitivity. The observed coordination behaviors derived from the spectroscopic analyses of the two MOF systems are compared to those predicted using space-filling models and relevant iron porphyrin molecular analogues. While the space-filling models show the ideal axial coordination behavior associated with these systems, the spectroscopic results provide powerful insight into the actual binding interactions that occur in practice. Evidence for potential side reactions occurring within the pores that may be responsible for the observed deviation from model coordination behavior in one of the MOF/guest molecule combinations is presented and discussed in the context of literature precedent.},
doi = {10.1021/acs.inorgchem.8b00117},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 6,
volume = 57,
place = {United States},
year = {2018},
month = {3}
}

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