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

Journal Article · · Inorganic Chemistry

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.

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 text January 2019
A Ligand Field Molecular Mechanics Study of CO 2 ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni) journal July 2019
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Computational Modeling of Transition Temperatures in Spin-Crossover Systems journal May 2019
CO 2 ‐Induced Spin‐State Switching at Room Temperature in a Monomeric Cobalt(II) Complex with the Porous Nature journal April 2020
CO 2 ‐Induced Spin‐State Switching at Room Temperature in a Monomeric Cobalt(II) Complex with the Porous Nature 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 journal May 2019
Deciphering crystal packing effects in the spin crossover of six [Fe II (2-pic) 3 ]Cl 2 solvatomorphs journal January 2019