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

doi:10.1021/acs.inorgchem.8b00502

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:

^[1];

^[1]

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

Publication Date:: 2018-08-01

Research Org.:: Lawrence Berkeley National Laboratory (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.

Copy to clipboard


                    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.

Copy to clipboard


                    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.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acs.inorgchem.8b00502

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

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
DOI: 10.1002/adts.201900098

Computational Modeling of Transition Temperatures in Spin-Crossover Systems
journal, May 2019

Cirera, Jordi; Ruiz, Eliseo
Comments on Inorganic Chemistry, Vol. 39, Issue 4
DOI: 10.1080/02603594.2019.1608967

Similar records in OSTI.GOV collections:

Theoretical Studies of Spin Crossover Metal-Organic Frameworks

Technical Report Paesani, Francesco

The research carried out within this grant focused on characterizing spin crossover (SCO) transitions, i.e., the change in spin state, in metal-organic frameworks (MOFs). MOFs are three-dimensional networks in which metal ions or clusters are connected to multidentate ligands. By combining high porosity, large surface area, guest selectivity, structural flexibility, and SCO properties, MOFs provide a promising platform for the development of multifunctional materials, such as molecular switches, memory devices, and chemical sensors. To characterize the SCO properties of MOFs at the molecular level, we have developed a hybrid Monte Carlo / molecular dynamics (MC/MD) method that builds upon themore »« less
DOI: 10.2172/1436510

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

Journal Article Southon, P. D. ; Liu, L. ; Fellows, E. A. ; ... - J. Am. Chem. Soc.

The nanoporous metal-organic framework [Fe(pz)Ni(CN){sub 4}], 1 (where pz is pyrazine), exhibits hysteretic spin-crossover at ambient conditions and is robust to the adsorption and desorption of a wide range of small molecular guests, both gases (N{sub 2}, O{sub 2}, CO{sub 2}) and vapors (methanol, ethanol, acetone, acetonitrile, and toluene). Through the comprehensive analysis of structure, host-guest properties, and spin-crossover behaviors, it is found that this pillared Hofmann system uniquely displays both guest-exchange-induced changes to spin-crossover and spin-crossover-induced changes to host-guest properties, with direct dynamic interplay between these two phenomena. Guest desorption and adsorption cause pronounced changes to the spin-crossover behaviormore »« less
DOI: 10.1021/ja902187d
Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks

Journal Article Elsaidi, Sameh K. ; Mohamed, Mona H. ; Simon, Cory M. ; ... - Chemical Science

The study of the mobility/rotation of the organic linkers in porous metal-organic frameworks could provide a valuable information about the guest/framework interaction and the factors control the kinetics of adsorption. Here, we analyzed the dynamics of pyrazine ring rotation in a series of pillared square grid frameworks, namely SIFSIX-3-M (M = Fe, Ni). It was found that the rotation of pyrazine ring is influenced by the variation of metal cation, temperature and the guest molecule. The Fe-analogue, [Fe(pz)2(SiF6)2] (pz= Pyrazine), , showed no pronounced ring rotation and exhibited a high affinity toward Xe gas over Kr as exemplified by themore »« less
DOI: 10.1039/c6sc05012c
Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis

Journal Article Yue, Yanfeng ; Fulvio, Pasquale F. ; Dai, Sheng - Accounts of Chemical Research

Metal–organic frameworks (MOFs) represent a new family of microporous materials; however, microporous–mesoporous hierarchical MOF materials have been less investigated because of the lack of simple, reliable methods to introduce mesopores to the crystalline microporous particles. State-of-the-art MOF hierarchical materials have been prepared by ligand extension methods or by using a template, resulting in intrinsic mesopores of longer ligands or replicated pores from template agents, respectively. However, mesoporous MOF materials obtained through ligand extension often collapse in the absence of guest molecules, which dramatically reduces the size of the pore aperture. Although the template-directed strategy allows for the preparation of hierarchicalmore »« less
Cited by 17
DOI: 10.1021/acs.accounts.5b00349

Full Text Available
First principles calculation of a large variation in dielectric tensor through the spin crossover in the CsFe[Cr(CN){sub 6}] Prussian blue analogue

Journal Article Middlemiss, Derek S., E-mail: derekmiddlemiss@gmail.com, E-mail: R.J.Deeth@warwick.ac.uk ; Deeth, Robert J., E-mail: derekmiddlemiss@gmail.com, E-mail: R.J.Deeth@warwick.ac.uk - Journal of Chemical Physics

The dielectric response of spin-crossover (SCO) materials is a key property facilitating their use in next-generation information processing technologies. Solid state hybrid density functional theory calculations show that the temperature-induced and strongly hysteretic SCO transition in the Cs{sup +}Fe{sup 2+}[Cr{sup 3+}(CN{sup −}){sub 6}] Prussian blue analogue (PBA) is associated with a large change (Δ) in both the static, Δε{sup 0}(HS − LS), and high frequency, Δε{sup ∞}(HS − LS) dielectric constants. The SCO-induced variation in CsFe[Cr(CN){sub 6}] is significantly greater than the experimental Δε values observed previously in other SCO materials. The phonon contribution, Δε{sup phon}(HS − LS), determined withinmore »« less
DOI: 10.1063/1.4869864

Similar Records

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

Abstract

Citation Formats

A Ligand Field Molecular Mechanics Study of CO 2 ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni) journal, July 2019

Computational Modeling of Transition Temperatures in Spin-Crossover Systems journal, May 2019

A Ligand Field Molecular Mechanics Study of CO ₂ ‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)
journal, July 2019

Computational Modeling of Transition Temperatures in Spin-Crossover Systems
journal, May 2019