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

Pham, C. Huy; Paesani, Francesco

doi:10.1021/acs.inorgchem.8b00502

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

Journal Article · 31 July 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b00502 · OSTI ID:1543619

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Univ. of California, San Diego, CA (United States)

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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1543619

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Computational Modeling of Transition Temperatures in Spin-Crossover Systems Cirera, Jordi; Ruiz, Eliseo Taylor & Francis https://doi.org/10.6084/m9.figshare.8175119	text	January 2019
A Ligand Field Molecular Mechanics Study of CO ₂ ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni) Melix, Patrick; Paesani, Francesco; Heine, Thomas Advanced Theory and Simulations, Vol. 2, Issue 11 https://doi.org/10.1002/adts.201900098	journal	July 2019
Molecular Spin Crossover Materials: Review of the Lattice Dynamical Properties Molnár, Gábor; Mikolasek, Mirko; Ridier, Karl Annalen der Physik, Vol. 531, Issue 10 https://doi.org/10.1002/andp.201900076	journal	August 2019
Computational Modeling of Transition Temperatures in Spin-Crossover Systems Cirera, Jordi; Ruiz, Eliseo Comments on Inorganic Chemistry, Vol. 39, Issue 4 https://doi.org/10.1080/02603594.2019.1608967	journal	May 2019
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CO ₂ ‐Induced Spin‐State Switching at Room Temperature in a Monomeric Cobalt(II) Complex with the Porous Nature Nakaya, Manabu; Kosaka, Wataru; Miyasaka, Hitoshi Angewandte Chemie International Edition, Vol. 59, Issue 26 https://doi.org/10.1002/anie.202003811	journal	April 2020
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 Sawczak, Mirosław; Jendrzejewski, Rafał; Maskowicz, Dominik European Journal of Inorganic Chemistry, Vol. 2019, Issue 27 https://doi.org/10.1002/ejic.201900231	journal	May 2019
Deciphering crystal packing effects in the spin crossover of six [Fe ^II (2-pic) ₃ ]Cl ₂ solvatomorphs Vela, Sergi; Paulsen, Hauke Dalton Transactions, Vol. 48, Issue 4 https://doi.org/10.1039/c8dt04394a	journal	January 2019

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