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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 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. https://doi.org/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. https://doi.org/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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Works referenced in this record:

Spin-Transition Polymers: From Molecular Materials Toward Memory Devices
journal, January 1998


Molecular spin crossover phenomenon: recent achievements and prospects
journal, January 2011

  • Bousseksou, Azzedine; Molnár, Gábor; Salmon, Lionel
  • Chemical Society Reviews, Vol. 40, Issue 6
  • DOI: 10.1039/c1cs15042a

Perturbation of Spin Crossover Behavior by Covalent Post-Synthetic Modification of a Porous Metal-Organic Framework
journal, July 2014

  • Clements, John E.; Price, Jason R.; Neville, Suzanne M.
  • Angewandte Chemie International Edition, Vol. 53, Issue 38
  • DOI: 10.1002/anie.201402951

Cooperative Spin Crossover Behavior in Cyanide-Bridged Fe(II)−M(II) Bimetallic 3D Hofmann-like Networks (M = Ni, Pd, and Pt)
journal, July 2001

  • Niel, Virginie; Martinez-Agudo, José María; Muñoz, M. Carmen
  • Inorganic Chemistry, Vol. 40, Issue 16
  • DOI: 10.1021/ic010259y

Elucidating the Mechanism of a Two-Step Spin Transition in a Nanoporous Metal−Organic Framework
journal, December 2008

  • Halder, Gregory J.; Chapman, Karena W.; Neville, Suzanne M.
  • Journal of the American Chemical Society, Vol. 130, Issue 51
  • DOI: 10.1021/ja8068038

Dynamic Interplay between Spin-Crossover and Host−Guest Function in a Nanoporous Metal−Organic Framework Material
journal, August 2009

  • Southon, Peter D.; Liu, Lang; Fellows, Elizabeth A.
  • Journal of the American Chemical Society, Vol. 131, Issue 31
  • DOI: 10.1021/ja902187d

Bidirectional Chemo-Switching of Spin State in a Microporous Framework
journal, June 2009

  • Ohba, Masaaki; Yoneda, Ko; Agustí, Gloria
  • Angewandte Chemie International Edition, Vol. 48, Issue 26
  • DOI: 10.1002/anie.200806039

Theoretical study on high-spin to low-spin transition of {Fe(pyrazine)[Pt(CN)4]}: Guest-induced entropy decrease
journal, August 2011


Hysteretic Three-Step Spin Crossover in a Thermo- and Photochromic 3D Pillared Hofmann-type Metal-Organic Framework
journal, September 2012

  • Sciortino, Natasha F.; Scherl-Gruenwald, Katrin R.; Chastanet, Guillaume
  • Angewandte Chemie International Edition, Vol. 51, Issue 40
  • DOI: 10.1002/anie.201204387

Reversible Chemisorption of Sulfur Dioxide in a Spin Crossover Porous Coordination Polymer
journal, October 2013

  • Arcís-Castillo, Zulema; Muñoz-Lara, Francisco J.; Muñoz, M. Carmen
  • Inorganic Chemistry, Vol. 52, Issue 21
  • DOI: 10.1021/ic4020477

Absorption of CO 2 and CS 2 into the Hofmann-Type Porous Coordination Polymer: Electrostatic versus Dispersion Interactions
journal, March 2013

  • Deshmukh, Milind Madhusudan; Ohba, Masaaki; Kitagawa, Susumu
  • Journal of the American Chemical Society, Vol. 135, Issue 12
  • DOI: 10.1021/ja400537f

Guest Modulation of Spin-Crossover Transition Temperature in a Porous Iron(II) Metal-Organic Framework: Experimental and Periodic DFT Studies
journal, August 2014

  • Aravena, Daniel; Castillo, Zulema Arcís; Muñoz, M. Carmen
  • Chemistry - A European Journal, Vol. 20, Issue 40
  • DOI: 10.1002/chem.201402292

Spin crossover intermediate plateau stabilization in a flexible 2-D Hofmann-type coordination polymer
journal, January 2014

  • Klein, Y. Maximilian; Sciortino, Natasha F.; Ragon, Florence
  • Chem. Commun., Vol. 50, Issue 29
  • DOI: 10.1039/C4CC01079E

Thermal Spin Crossover Behaviour of Two-Dimensional Hofmann-Type Coordination Polymers Incorporating Photoactive Ligands
journal, January 2014

  • Ragon, Florence; Yaksi, Korcan; Sciortino, Natasha F.
  • Australian Journal of Chemistry, Vol. 67, Issue 11
  • DOI: 10.1071/CH14188

An Investigation of Photo- and Pressure-Induced Effects in a Pair of Isostructural Two-Dimensional Spin-Crossover Framework Materials
journal, May 2014

  • Sciortino, Natasha F.; Neville, Suzanne M.; Desplanches, Cédric
  • Chemistry - A European Journal, Vol. 20, Issue 24
  • DOI: 10.1002/chem.201400367

Thermal- and Light-Induced Spin-Crossover Bistability in a Disrupted Hofmann-Type 3D Framework
journal, July 2014

  • Sciortino, Natasha F.; Neville, Suzanne M.; Létard, Jean-François
  • Inorganic Chemistry, Vol. 53, Issue 15
  • DOI: 10.1021/ic500323r

Reversible Guest Binding in a Non-Porous Fe II Coordination Polymer Host Toggles Spin Crossover
journal, September 2015

  • Lennartson, Anders; Southon, Peter; Sciortino, Natasha F.
  • Chemistry - A European Journal, Vol. 21, Issue 45
  • DOI: 10.1002/chem.201502547

Hysteretic Four-Step Spin Crossover within a Three-Dimensional Porous Hofmann-like Material
journal, October 2016

  • Clements, John E.; Price, Jason R.; Neville, Suzanne M.
  • Angewandte Chemie International Edition, Vol. 55, Issue 48
  • DOI: 10.1002/anie.201605418

Exploiting Pressure To Induce a “Guest-Blocked” Spin Transition in a Framework Material
journal, September 2016


Spin crossover-induced colossal positive and negative thermal expansion in a nanoporous coordination framework material
journal, October 2017

  • Mullaney, Benjamin R.; Goux-Capes, Laurence; Price, David J.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-00776-1

Guest Programmable Multistep Spin Crossover in a Porous 2-D Hofmann-Type Material
journal, January 2017

  • Murphy, Michael J.; Zenere, Katrina A.; Ragon, Florence
  • Journal of the American Chemical Society, Vol. 139, Issue 3
  • DOI: 10.1021/jacs.6b12465

High Spin to Low Spin Relaxation Regime Change in a Multistep 3D Spin-Crossover Material: High Spin to Low Spin Relaxation Regime Change in a Multistep 3D Spin-Crossover Material
journal, January 2018

  • Chastanet, Guillaume; Sciortino, Natasha F.; Neville, Suzanne M.
  • European Journal of Inorganic Chemistry, Vol. 2018, Issue 3-4
  • DOI: 10.1002/ejic.201701127

Theoretical Modeling of Spin Crossover in Metal–Organic Frameworks: [Fe(pz) 2 Pt(CN) 4 ] as a Case Study
journal, September 2014

  • Cirera, Jordi; Babin, Volodymyr; Paesani, Francesco
  • Inorganic Chemistry, Vol. 53, Issue 20
  • DOI: 10.1021/ic501519a

The ligand field molecular mechanics model and the stereoelectronic effects of d and s electrons
journal, February 2001


Molecular modelling for transition metal complexes: Dealing with d-electron effects
journal, March 2009

  • Deeth, Robert J.; Anastasi, Anna; Diedrich, Christian
  • Coordination Chemistry Reviews, Vol. 253, Issue 5-6
  • DOI: 10.1016/j.ccr.2008.06.018

Molecular Mechanisms of Spin Crossover in the {Fe(pz)[Pt(CN) 4 ]} Metal–Organic Framework upon Water Adsorption
journal, May 2016

  • Pham, C. Huy; Cirera, Jordi; Paesani, Francesco
  • Journal of the American Chemical Society, Vol. 138, Issue 19
  • DOI: 10.1021/jacs.6b02564

Spin Crossover in the {Fe(pz)[Pt(CN) 4 ]} Metal–Organic Framework upon Pyrazine Adsorption
journal, September 2016


Molecular-Level Characterization of the Breathing Behavior of the Jungle-Gym-type DMOF-1 Metal–Organic Framework
journal, February 2012

  • Grosch, Jason S.; Paesani, Francesco
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja2100615

A Switchable Molecular Rotator: Neutron Spectroscopy Study on a Polymeric Spin-Crossover Compound
journal, March 2012

  • Rodríguez-Velamazán, J. Alberto; González, Miguel A.; Real, José A.
  • Journal of the American Chemical Society, Vol. 134, Issue 11
  • DOI: 10.1021/ja206228n

XSEDE: Accelerating Scientific Discovery
journal, September 2014

  • Towns, John; Cockerill, Timothy; Dahan, Maytal
  • Computing in Science & Engineering, Vol. 16, Issue 5
  • DOI: 10.1109/MCSE.2014.80

Works referencing / citing this record:

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
  • DOI: 10.1002/andp.201900076

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
  • DOI: 10.1002/anie.202003811

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
  • DOI: 10.1002/adts.201900098

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
  • DOI: 10.1039/c8dt04394a

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

  • Nakaya, Manabu; Kosaka, Wataru; Miyasaka, Hitoshi
  • Angewandte Chemie, Vol. 132, Issue 26
  • DOI: 10.1002/ange.202003811

Computational Modeling of Transition Temperatures in Spin-Crossover Systems
text, January 2019