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Title: Guest-Dependent Stabilization of the Low-Spin State in Spin-Crossover Metal-Organic Frameworks

Abstract

Computer simulations are carried out to characterize the variation of spin-crossover (SCO) behavior of the prototypical {Fe(pz)[Pt(CN) 4]} metal-organic framework (MOF) upon adsorption of chemically and structurally different guest molecules. A detailed analysis of both strength and anisotropy of guest molecule–framework interactions reveals direct correlations between the mobility of the guest molecules inside the MOF pores, the rotational mobility of the pyrazine rings of the framework, and the stabilization of the low-spin state of the material. On the basis of these correlations, precise molecular criteria are established for predicting the spin state of {Fe(pz)[Pt(CN) 4]} upon guest adsorption. Finally, predictions of the SCO temperature upon adsorption of various toxic gases demonstrate that in silico modeling can provide fundamental insights and design principles for the development of spin-crossover MOFs for applications in gas detection and chemical sensing.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543619
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 16; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Pham, C. Huy, and Paesani, Francesco. Guest-Dependent Stabilization of the Low-Spin State in Spin-Crossover Metal-Organic Frameworks. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b00502.
Pham, C. Huy, & Paesani, Francesco. Guest-Dependent Stabilization of the Low-Spin State in Spin-Crossover Metal-Organic Frameworks. United States. doi:10.1021/acs.inorgchem.8b00502.
Pham, C. Huy, and Paesani, Francesco. Wed . "Guest-Dependent Stabilization of the Low-Spin State in Spin-Crossover Metal-Organic Frameworks". United States. doi:10.1021/acs.inorgchem.8b00502. https://www.osti.gov/servlets/purl/1543619.
@article{osti_1543619,
title = {Guest-Dependent Stabilization of the Low-Spin State in Spin-Crossover Metal-Organic Frameworks},
author = {Pham, C. Huy and Paesani, Francesco},
abstractNote = {Computer simulations are carried out to characterize the variation of spin-crossover (SCO) behavior of the prototypical {Fe(pz)[Pt(CN)4]} metal-organic framework (MOF) upon adsorption of chemically and structurally different guest molecules. A detailed analysis of both strength and anisotropy of guest molecule–framework interactions reveals direct correlations between the mobility of the guest molecules inside the MOF pores, the rotational mobility of the pyrazine rings of the framework, and the stabilization of the low-spin state of the material. On the basis of these correlations, precise molecular criteria are established for predicting the spin state of {Fe(pz)[Pt(CN)4]} upon guest adsorption. Finally, predictions of the SCO temperature upon adsorption of various toxic gases demonstrate that in silico modeling can provide fundamental insights and design principles for the development of spin-crossover MOFs for applications in gas detection and chemical sensing.},
doi = {10.1021/acs.inorgchem.8b00502},
journal = {Inorganic Chemistry},
number = 16,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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A Ligand Field Molecular Mechanics Study of CO 2 ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)
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