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:
-
- Univ. of California, San Diego, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (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}
}
Web of Science
Works referencing / citing this record:
A Ligand Field Molecular Mechanics Study of CO 2 ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)
journal, July 2019
- Melix, Patrick; Paesani, Francesco; Heine, Thomas
- Advanced Theory and Simulations, Vol. 2, Issue 11
Computational Modeling of Transition Temperatures in Spin-Crossover Systems
journal, May 2019
- Cirera, Jordi; Ruiz, Eliseo
- Comments on Inorganic Chemistry, Vol. 39, Issue 4
A Ligand Field Molecular Mechanics Study of CO 2 ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)
journal, July 2019
- Melix, Patrick; Paesani, Francesco; Heine, Thomas
- Advanced Theory and Simulations, Vol. 2, Issue 11
Computational Modeling of Transition Temperatures in Spin-Crossover Systems
journal, May 2019
- Cirera, Jordi; Ruiz, Eliseo
- Comments on Inorganic Chemistry, Vol. 39, Issue 4
CO 2 ‐Induced Spin‐State Switching at Room Temperature in a Monomeric Cobalt(II) Complex with the Porous Nature
journal, April 2020
- Nakaya, Manabu; Kosaka, Wataru; Miyasaka, Hitoshi
- Angewandte Chemie International Edition, Vol. 59, Issue 26
Molecular Spin Crossover Materials: Review of the Lattice Dynamical Properties
journal, August 2019
- Molnár, Gábor; Mikolasek, Mirko; Ridier, Karl
- Annalen der Physik, Vol. 531, Issue 10
Nanocrystalline Polymer Impregnated [Fe(pz)Pt(CN) 4 ] Thin Films Prepared by Matrix-Assisted Pulsed Laser Evaporation: Nanocrystalline Polymer Impregnated [Fe(pz)Pt(CN) 4 ] Thin Films Prepared by Matrix-Assisted Pulsed Laser Evaporation
journal, May 2019
- Sawczak, Mirosław; Jendrzejewski, Rafał; Maskowicz, Dominik
- European Journal of Inorganic Chemistry, Vol. 2019, Issue 27
Deciphering crystal packing effects in the spin crossover of six [Fe II (2-pic) 3 ]Cl 2 solvatomorphs
journal, January 2019
- Vela, Sergi; Paulsen, Hauke
- Dalton Transactions, Vol. 48, Issue 4