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

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

Journal Article · Wed Aug 01 00:00:00 EDT 2018 · Inorganic Chemistry

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

^[1]; ^[1]

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.

View Accepted Manuscript (DOE)

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

References (31)

Spin‐Crossover Materials Halcrow, Malcolm A. https://doi.org/10.1002/9781118519301	book	January 2013
Bidirectional Chemo-Switching of Spin State in a Microporous Framework Ohba, Masaaki; Yoneda, Ko; Agustí, Gloria Angewandte Chemie International Edition, Vol. 48, Issue 26 https://doi.org/10.1002/anie.200806039	journal	June 2009
Hysteretic Three-Step Spin Crossover in a Thermo- and Photochromic 3D Pillared Hofmann-type Metal-Organic Framework Sciortino, Natasha F.; Scherl-Gruenwald, Katrin R.; Chastanet, Guillaume Angewandte Chemie International Edition, Vol. 51, Issue 40 https://doi.org/10.1002/anie.201204387	journal	September 2012
Perturbation of Spin Crossover Behavior by Covalent Post-Synthetic Modification of a Porous Metal-Organic Framework Clements, John E.; Price, Jason R.; Neville, Suzanne M. Angewandte Chemie International Edition, Vol. 53, Issue 38 https://doi.org/10.1002/anie.201402951	journal	July 2014
Hysteretic Four-Step Spin Crossover within a Three-Dimensional Porous Hofmann-like Material Clements, John E.; Price, Jason R.; Neville, Suzanne M. Angewandte Chemie International Edition, Vol. 55, Issue 48 https://doi.org/10.1002/anie.201605418	journal	October 2016
An Investigation of Photo- and Pressure-Induced Effects in a Pair of Isostructural Two-Dimensional Spin-Crossover Framework Materials Sciortino, Natasha F.; Neville, Suzanne M.; Desplanches, Cédric Chemistry - A European Journal, Vol. 20, Issue 24 https://doi.org/10.1002/chem.201400367	journal	May 2014
Guest Modulation of Spin-Crossover Transition Temperature in a Porous Iron(II) Metal-Organic Framework: Experimental and Periodic DFT Studies Aravena, Daniel; Castillo, Zulema Arcís; Muñoz, M. Carmen Chemistry - A European Journal, Vol. 20, Issue 40 https://doi.org/10.1002/chem.201402292	journal	August 2014
Reversible Guest Binding in a Non-Porous Fe ^II Coordination Polymer Host Toggles Spin Crossover Lennartson, Anders; Southon, Peter; Sciortino, Natasha F. Chemistry - A European Journal, Vol. 21, Issue 45 https://doi.org/10.1002/chem.201502547	journal	September 2015
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 Chastanet, Guillaume; Sciortino, Natasha F.; Neville, Suzanne M. European Journal of Inorganic Chemistry, Vol. 2018, Issue 3-4 https://doi.org/10.1002/ejic.201701127	journal	January 2018
The ligand field molecular mechanics model and the stereoelectronic effects of d and s electrons Deeth, R. Coordination Chemistry Reviews, Vol. 212, Issue 1 https://doi.org/10.1016/S0010-8545(00)00354-4	journal	February 2001
Molecular modelling for transition metal complexes: Dealing with d-electron effects Deeth, Robert J.; Anastasi, Anna; Diedrich, Christian Coordination Chemistry Reviews, Vol. 253, Issue 5-6 https://doi.org/10.1016/j.ccr.2008.06.018	journal	March 2009
Theoretical study on high-spin to low-spin transition of {Fe(pyrazine)[Pt(CN)4]}: Guest-induced entropy decrease Ando, Hideo; Nakao, Yoshihide; Sato, Hirofumi Chemical Physics Letters, Vol. 511, Issue 4-6 https://doi.org/10.1016/j.cplett.2011.06.084	journal	August 2011
Exploiting Pressure To Induce a “Guest-Blocked” Spin Transition in a Framework Material Sciortino, Natasha F.; Ragon, Florence; Zenere, Katrina A. Inorganic Chemistry, Vol. 55, Issue 20 https://doi.org/10.1021/acs.inorgchem.6b01686	journal	September 2016
Spin Crossover in the {Fe(pz)[Pt(CN) ₄ ]} Metal–Organic Framework upon Pyrazine Adsorption Pham, C. Huy; Paesani, Francesco The Journal of Physical Chemistry Letters, Vol. 7, Issue 19 https://doi.org/10.1021/acs.jpclett.6b01788	journal	September 2016
Cooperative Spin Crossover Behavior in Cyanide-Bridged Fe(II)−M(II) Bimetallic 3D Hofmann-like Networks (M = Ni, Pd, and Pt) Niel, Virginie; Martinez-Agudo, José María; Muñoz, M. Carmen Inorganic Chemistry, Vol. 40, Issue 16 https://doi.org/10.1021/ic010259y	journal	July 2001
Reversible Chemisorption of Sulfur Dioxide in a Spin Crossover Porous Coordination Polymer Arcís-Castillo, Zulema; Muñoz-Lara, Francisco J.; Muñoz, M. Carmen Inorganic Chemistry, Vol. 52, Issue 21 https://doi.org/10.1021/ic4020477	journal	October 2013
Thermal- and Light-Induced Spin-Crossover Bistability in a Disrupted Hofmann-Type 3D Framework Sciortino, Natasha F.; Neville, Suzanne M.; Létard, Jean-François Inorganic Chemistry, Vol. 53, Issue 15 https://doi.org/10.1021/ic500323r	journal	July 2014
Theoretical Modeling of Spin Crossover in Metal–Organic Frameworks: [Fe(pz) ₂ Pt(CN) ₄ ] as a Case Study Cirera, Jordi; Babin, Volodymyr; Paesani, Francesco Inorganic Chemistry, Vol. 53, Issue 20 https://doi.org/10.1021/ic501519a	journal	September 2014
A Switchable Molecular Rotator: Neutron Spectroscopy Study on a Polymeric Spin-Crossover Compound Rodríguez-Velamazán, J. Alberto; González, Miguel A.; Real, José A. Journal of the American Chemical Society, Vol. 134, Issue 11 https://doi.org/10.1021/ja206228n	journal	March 2012
Molecular-Level Characterization of the Breathing Behavior of the Jungle-Gym-type DMOF-1 Metal–Organic Framework Grosch, Jason S.; Paesani, Francesco Journal of the American Chemical Society, Vol. 134, Issue 9 https://doi.org/10.1021/ja2100615	journal	February 2012
Absorption of CO ₂ and CS ₂ into the Hofmann-Type Porous Coordination Polymer: Electrostatic versus Dispersion Interactions Deshmukh, Milind Madhusudan; Ohba, Masaaki; Kitagawa, Susumu Journal of the American Chemical Society, Vol. 135, Issue 12 https://doi.org/10.1021/ja400537f	journal	March 2013
Elucidating the Mechanism of a Two-Step Spin Transition in a Nanoporous Metal−Organic Framework Halder, Gregory J.; Chapman, Karena W.; Neville, Suzanne M. Journal of the American Chemical Society, Vol. 130, Issue 51 https://doi.org/10.1021/ja8068038	journal	December 2008
Dynamic Interplay between Spin-Crossover and Host−Guest Function in a Nanoporous Metal−Organic Framework Material Southon, Peter D.; Liu, Lang; Fellows, Elizabeth A. Journal of the American Chemical Society, Vol. 131, Issue 31 https://doi.org/10.1021/ja902187d	journal	August 2009
Molecular Mechanisms of Spin Crossover in the {Fe(pz)[Pt(CN) ₄ ]} Metal–Organic Framework upon Water Adsorption Pham, C. Huy; Cirera, Jordi; Paesani, Francesco Journal of the American Chemical Society, Vol. 138, Issue 19 https://doi.org/10.1021/jacs.6b02564	journal	May 2016
Guest Programmable Multistep Spin Crossover in a Porous 2-D Hofmann-Type Material Murphy, Michael J.; Zenere, Katrina A.; Ragon, Florence Journal of the American Chemical Society, Vol. 139, Issue 3 https://doi.org/10.1021/jacs.6b12465	journal	January 2017
Spin crossover-induced colossal positive and negative thermal expansion in a nanoporous coordination framework material Mullaney, Benjamin R.; Goux-Capes, Laurence; Price, David J. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00776-1	journal	October 2017
Spin crossover intermediate plateau stabilization in a flexible 2-D Hofmann-type coordination polymer Klein, Y. Maximilian; Sciortino, Natasha F.; Ragon, Florence Chem. Commun., Vol. 50, Issue 29 https://doi.org/10.1039/C4CC01079E	journal	January 2014
Molecular spin crossover phenomenon: recent achievements and prospects Bousseksou, Azzedine; Molnár, Gábor; Salmon, Lionel Chemical Society Reviews, Vol. 40, Issue 6 https://doi.org/10.1039/c1cs15042a	journal	January 2011
Thermal Spin Crossover Behaviour of Two-Dimensional Hofmann-Type Coordination Polymers Incorporating Photoactive Ligands Ragon, Florence; Yaksi, Korcan; Sciortino, Natasha F. Australian Journal of Chemistry, Vol. 67, Issue 11 https://doi.org/10.1071/CH14188	journal	January 2014
XSEDE: Accelerating Scientific Discovery Towns, John; Cockerill, Timothy; Dahan, Maytal Computing in Science & Engineering, Vol. 16, Issue 5 https://doi.org/10.1109/MCSE.2014.80	journal	September 2014
Spin-Transition Polymers: From Molecular Materials Toward Memory Devices Kahn, O. Science, Vol. 279, Issue 5347 https://doi.org/10.1126/science.279.5347.44	journal	January 1998

Cited By (8)

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
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, Vol. 132, Issue 26 https://doi.org/10.1002/ange.202003811	journal	April 2020
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
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
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

Similar Records

Theoretical Studies of Spin Crossover Metal-Organic Frameworks

Technical Report · Sat Jun 01 00:00:00 EDT 2013 · OSTI ID:1436510

Dynamic interplay between spin-crossover and host-guest function in a nanoporous metal-organic framework material.

Journal Article · Wed Dec 31 23:00:00 EST 2008 · J. Am. Chem. Soc. · OSTI ID:963640

Guest tunable structure and spin crossover properties in a nanoporous coordination framework material.

Journal Article · Tue Aug 11 00:00:00 EDT 2009 · J. Am. Chem. Soc. · OSTI ID:1008271

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry

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

Citation Formats

References (31)

Cited By (8)

Similar Records

Related Subjects