Crystal engineering, structure–function relationships, and the future of metal–organic frameworks

Allendorf, Mark D.; Stavila, Vitalie

doi:10.1039/C4CE01693A

Title: Crystal engineering, structure–function relationships, and the future of metal–organic frameworks

Journal Article · Wed Oct 15 00:00:00 EDT 2014 · CrystEngComm

DOI:https://doi.org/10.1039/C4CE01693A· OSTI ID:1184502

Allendorf, Mark D. ^[1]; Stavila, Vitalie ^[1]

Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Metal-Organic Frameworks (MOFs) are a rapidly expanding class of hybrid organic-inorganic materials that can be rationally designed and assembled through crystal engineering. The explosion of interest in this subclass of coordination polymers results from their outstanding properties and myriad possible applications that include traditional uses of microporous materials, such as gas storage, separations, and catalysis, to new realms in biomedicine, electronic devices, and and information storage. The objective of this Highlight article is to provide the reader with a sense of where the field stands after roughly fifteen years of research. Remarkable progress has been made, but the barriers to practical and commercial advances are also illuminated. We discuss the basic elements of MOF assembly and present a conceptual hierarchy of structural elements that assists in understanding how unique properties in these materials can be achieved. Structure-function relationships are then discussed; several are now well understood as a result of the focused efforts of many research groups over the past decade. Prospects for practical applications of MOFs in membranes, catalysis, biomedicine, and as active components in electronic and photonic devices are also discussed. Finally, we list key challenges that, in our view, must be addressed for these materials to realize their full potential in the marketplace.

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Research Organization:: Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1184502

Report Number(s):: SAND-2014-19073J; CRECF4; 540693

Journal Information:: CrystEngComm, Vol. 17, Issue 2; ISSN 1466-8033

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 216 works

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Pt Nanoclusters Confined within Metal–Organic Framework Cavities for Chemoselective Cinnamaldehyde Hydrogenation Guo, Zhiyong; Xiao, Chaoxian; Maligal-Ganesh, Raghu V. ACS Catalysis, Vol. 4, Issue 5, p. 1340-1348 https://doi.org/10.1021/cs400982n	journal	April 2014
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Cyclometalated metal–organic frameworks as stable and reusable heterogeneous catalysts for allylic N-alkylation of amines Dau, Phuong V.; Cohen, Seth M. Chemical Communications, Vol. 49, Issue 55 https://doi.org/10.1039/c3cc42119h	journal	January 2013
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Stress-Induced Chemical Detection Using Flexible Metal−Organic Frameworks Allendorf, Mark D.; Houk, Ronald J. T.; Andruszkiewicz, Leanne Journal of the American Chemical Society, Vol. 130, Issue 44, p. 14404-14405 https://doi.org/10.1021/ja805235k	journal	November 2008
Metal–Organic Framework Materials as Chemical Sensors Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K. Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125 https://doi.org/10.1021/cr200324t	journal	September 2011
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Kinetics and mechanism of metal–organic framework thin film growth: systematic investigation of HKUST-1 deposition on QCM electrodes Stavila, Vitalie; Volponi, Joanne; Katzenmeyer, Aaron M. Chemical Science, Vol. 3, Issue 5 https://doi.org/10.1039/c2sc20065a	journal	January 2012
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Patterned Deposition of Metal-Organic Frameworks onto Plastic, Paper, and Textile Substrates by Inkjet Printing of a Precursor Solution Zhuang, Jin-Liang; Ar, Deniz; Yu, Xiu-Jun Advanced Materials, Vol. 25, Issue 33 https://doi.org/10.1002/adma.201301626	journal	June 2013
Metal-Organic Framework ZIF-8 Films As Low-κ Dielectrics in Microelectronics Eslava, Salvador; Zhang, Liping; Esconjauregui, Santiago Chemistry of Materials, Vol. 25, Issue 1 https://doi.org/10.1021/cm302610z	journal	December 2012
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Electroconductive Porous Coordination Polymer Cu[Cu(pdt) ₂ ] Composed of Donor and Acceptor Building Units Takaishi, Shinya; Hosoda, Miyuki; Kajiwara, Takashi Inorganic Chemistry, Vol. 48, Issue 19 https://doi.org/10.1021/ic802117q	journal	October 2009
High Electrical Conductivity in Ni ₃ (2,3,6,7,10,11-hexaiminotriphenylene) ₂ , a Semiconducting Metal–Organic Graphene Analogue Sheberla, Dennis; Sun, Lei; Blood-Forsythe, Martin A. Journal of the American Chemical Society, Vol. 136, Issue 25 https://doi.org/10.1021/ja502765n	journal	April 2014
High Charge Mobility in a Tetrathiafulvalene-Based Microporous Metal–Organic Framework Narayan, Tarun C.; Miyakai, Tomoyo; Seki, Shu Journal of the American Chemical Society, Vol. 134, Issue 31 https://doi.org/10.1021/ja3059827	journal	July 2012
Mn ₂ (2,5-disulfhydrylbenzene-1,4-dicarboxylate): A Microporous Metal–Organic Framework with Infinite (−Mn–S−) _∞ Chains and High Intrinsic Charge Mobility Sun, Lei; Miyakai, Tomoyo; Seki, Shu Journal of the American Chemical Society, Vol. 135, Issue 22 https://doi.org/10.1021/ja4037516	journal	May 2013
Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices Talin, A. Alec; Centrone, Andrea; Ford, Alexandra C. Science, Vol. 343, Issue 6166, p. 66-69 https://doi.org/10.1126/science.1246738	journal	December 2013
MOFs as proton conductors – challenges and opportunities Ramaswamy, Padmini; Wong, Norman E.; Shimizu, George K. H. Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00093E	journal	January 2014
Anhydrous proton conduction at 150 °C in a crystalline metal–organic framework Hurd, Jeff A.; Vaidhyanathan, Ramanathan; Thangadurai, Venkataraman Nature Chemistry, Vol. 1, Issue 9 https://doi.org/10.1038/nchem.402	journal	October 2009
Ionic Conductivity in the Metal-Organic Framework UiO-66 by Dehydration and Insertion of Lithium tert -Butoxide Ameloot, Rob; Aubrey, Michael; Wiers, Brian M. Chemistry - A European Journal, Vol. 19, Issue 18 https://doi.org/10.1002/chem.201300326	journal	March 2013
Transported into fuel cells Kitagawa, Hiroshi Nature Chemistry, Vol. 1, Issue 9 https://doi.org/10.1038/nchem.454	journal	December 2009
Proton Conductivity in Doped Aluminum Phosphonate Sponges Wegener, Jennifer; Kaltbeitzel, Anke; Graf, Robert ChemSusChem, Vol. 7, Issue 4 https://doi.org/10.1002/cssc.201301055	journal	February 2014
Biomedical Applications of Metal Organic Frameworks Keskin, Seda; Kızılel, Seda Industrial & Engineering Chemistry Research, Vol. 50, Issue 4 https://doi.org/10.1021/ie101312k	journal	February 2011
Postsynthetic diazeniumdiolate formation and NO release from MOFs Nguyen, Joseph G.; Tanabe, Kristine K.; Cohen, Seth M. CrystEngComm, Vol. 12, Issue 8 https://doi.org/10.1039/c000154f	journal	January 2010
Exceptional Behavior over the Whole Adsorption−Storage−Delivery Cycle for NO in Porous Metal Organic Frameworks McKinlay, Alistair C.; Xiao, Bo; Wragg, David S. Journal of the American Chemical Society, Vol. 130, Issue 31 https://doi.org/10.1021/ja801997r	journal	August 2008
Metal–Organic Frameworks as Efficient Materials for Drug Delivery Horcajada, Patricia; Serre, Christian; Vallet-Regí, María Angewandte Chemie International Edition, Vol. 45, Issue 36, p. 5974-5978 https://doi.org/10.1002/anie.200601878	journal	September 2006
Cation-Triggered Drug Release from a Porous Zinc−Adeninate Metal−Organic Framework An, Jihyun; Geib, Steven J.; Rosi, Nathaniel L. Journal of the American Chemical Society, Vol. 131, Issue 24 https://doi.org/10.1021/ja902972w	journal	June 2009
Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging Horcajada, Patricia; Chalati, Tamim; Serre, Christian Nature Materials, Vol. 9, Issue 2 https://doi.org/10.1038/nmat2608	journal	December 2009
Relaxometry Studies of a Highly Stable Nanoscale Metal–Organic Framework Made of Cu(II), Gd(III), and the Macrocyclic DOTP Carné-Sánchez, Arnau; Bonnet, Célia S.; Imaz, Inhar Journal of the American Chemical Society, Vol. 135, Issue 47 https://doi.org/10.1021/ja4094378	journal	November 2013
Metal–Organic Frameworks as Sensory Materials and Imaging Agents Liu, Demin; Lu, Kuangda; Poon, Christopher Inorganic Chemistry, Vol. 53, Issue 4 https://doi.org/10.1021/ic402194c	journal	November 2013
The Biocompatibility of Metal–Organic Framework Coatings: An Investigation on the Stability of SURMOFs with Regard to Water and Selected Cell Culture Media Hanke, Maximilian; Arslan, Hasan K.; Bauer, Stella Langmuir, Vol. 28, Issue 17 https://doi.org/10.1021/la300457z	journal	April 2012
Exceptional Negative Thermal Expansion in Isoreticular Metal–Organic Frameworks Dubbeldam, David; Walton, Krista S.; Ellis, Donald E. Angewandte Chemie, Vol. 119, Issue 24 https://doi.org/10.1002/ange.200700218	journal	June 2007
Hydrogen Storage in Metal-Organic Frameworks Zou, Lanfang; Zhou, Hong-Cai Nanostructured Materials for Next-Generation Energy Storage and Conversion https://doi.org/10.1007/978-3-662-53514-1_5	book	December 2016
Metal–Organic Frameworks as Efficient Materials for Drug Delivery Horcajada, Patricia; Serre, Christian; Vallet-Regí, María Angewandte Chemie, Vol. 118, Issue 36 https://doi.org/10.1002/ange.200601878	journal	September 2006
Binary Janus Porous Coordination Polymer Coatings for Sensor Devices with Tunable Analyte Affinity Meilikhov, Mikhail; Furukawa, Shuhei; Hirai, Kenji Angewandte Chemie, Vol. 125, Issue 1 https://doi.org/10.1002/ange.201207320	journal	November 2012
Nanoscale Metal–Organic Frameworks for Biomedical Imaging and Drug Delivery Wenbin, Lin,; Joseph, Della Rocca,; Demin, Liu, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/q7c0-kf53	text	January 2011
Hydrogen Storage in Metal-Organic Frameworks Huang, Yue; Ke, San Huang Applied Mechanics and Materials, Vol. 316-317 https://doi.org/10.4028/www.scientific.net/amm.316-317.946	journal	April 2013

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Carboxylate-Hydrazone Mixed-Linker Metal-Organic Frameworks: Synthesis, Structure, and Selective Gas Adsorption: Carboxylate-Hydrazone Mixed-Linker Metal-Organic Frameworks: Synthesis, Structure, and Selective Gas Adsorption Roztocki, Kornel; Senkovska, Irena; Kaskel, Stefan European Journal of Inorganic Chemistry, Vol. 2016, Issue 27 https://doi.org/10.1002/ejic.201600134	journal	April 2016
Reviewing Rare Earth Succinate Frameworks from the Reticular Chemistry Point of View: Structures, Nets, Catalytic and Photoluminescence Applications Bernini, Maria C.; Gomez, Germán E.; Brusau, Elena V. Israel Journal of Chemistry, Vol. 58, Issue 9-10 https://doi.org/10.1002/ijch.201800095	journal	September 2018
Halogen⋅⋅⋅π Interactions in Supramolecular Architecture of 1D Coordination Polymers and Their Electrical Conductance Islam, Sakhiul; Datta, Joydeep; Maity, Suvendu ChemistrySelect, Vol. 4, Issue 12 https://doi.org/10.1002/slct.201900578	journal	March 2019
Effects of Anionic Geometries on Hydrogen-Bonding Networks of 1-(4-pyridyl) Piperazine Chen, Fu; Wang, Shi; Li, Yong-Hua Journal of Chemical Crystallography, Vol. 46, Issue 6-7 https://doi.org/10.1007/s10870-016-0662-y	journal	July 2016
Controlled partial interpenetration in metal–organic frameworks Ferguson, Alan; Liu, Lujia; Tapperwijn, Stefanus J. Nature Chemistry, Vol. 8, Issue 3 https://doi.org/10.1038/nchem.2430	journal	January 2016
Four binuclear coordination polymers with a 6 ³ net and self-assembly of 2D 6 ³ topology into different supramolecular networks using unit–unit H-bonds Xu, Guohai; Xie, Min; Li, Xiaokang CrystEngComm, Vol. 17, Issue 19 https://doi.org/10.1039/c5ce00264h	journal	January 2015
Mononuclear and polynuclear complexes ligated by an iminodiacetic acid derivative: synthesis, structure, solution studies and magnetic properties Puentes, Roberto; Torres, Julia; Kremer, Carlos Dalton Transactions, Vol. 45, Issue 12 https://doi.org/10.1039/c5dt05060j	journal	January 2016
Tunable luminescence and white light emission of mixed lanthanide–organic frameworks based on polycarboxylate ligands Wu, Jiawei; Zhang, Huabin; Du, Shaowu Journal of Materials Chemistry C, Vol. 4, Issue 16 https://doi.org/10.1039/c5tc04432d	journal	January 2016
Zn( ii )-based metal–organic framework: an exceptionally thermally stable, guest-free low dielectric material Mendiratta, Shruti; Usman, Muhammad; Chang, Chun-Chi Journal of Materials Chemistry C, Vol. 5, Issue 6 https://doi.org/10.1039/c6tc05314a	journal	January 2017
Sensing properties, energy transfer mechanism and tuneable particle size processing of luminescent two-dimensional rare earth coordination networks Godoy, Agustín A.; Gomez, Germán E.; Kaczmarek, Anna M. Journal of Materials Chemistry C, Vol. 5, Issue 47 https://doi.org/10.1039/c7tc04006g	journal	January 2017
Bulky substituent and solvent-induced alternative nodes for layered Cd–isophthalate/acylhydrazone frameworks Roztocki, Kornel; Lupa, Magdalena; Hodorowicz, Maciej CrystEngComm, Vol. 20, Issue 20 https://doi.org/10.1039/c8ce00269j	journal	January 2018
Recent advances and opportunities in the treatment of hydrocarbons and oils: Metal-organic frameworks-based approaches Kumar, Vanish; Vellingiri, Kowsalya; Kukkar, Deepak Critical Reviews in Environmental Science and Technology, Vol. 49, Issue 7 https://doi.org/10.1080/10643389.2018.1554402	journal	January 2019
The right isotherms for the right reasons? Validation of generic force fields for prediction of methane adsorption in metal-organic frameworks Lennox, Matthew J.; Bound, Michelle; Henley, Alice Taylor & Francis https://doi.org/10.6084/m9.figshare.4753837	text	January 2017
Engineered MOFs and Enzymes for the Synthesis of Active Pharmaceutical Ingredients Cirujano, Francisco G. ChemCatChem, Vol. 11, Issue 23 https://doi.org/10.1002/cctc.201900131	journal	March 2019
Role of Anions in Assembling the Coordination Polymers of Bis-pyridyl-alkanediamides Suman, Kumari; Khullar, Sadhika; Mandal, Sanjay K. ChemistrySelect, Vol. 1, Issue 21 https://doi.org/10.1002/slct.201601249	journal	December 2016
Regulation of the Degree of Interpenetration in Metal–Organic Frameworks Verma, Gaurav; Butikofer, Sydney; Kumar, Sanjay Topics in Current Chemistry, Vol. 378, Issue 1 https://doi.org/10.1007/s41061-019-0268-x	journal	December 2019
Sequential dielectric phase transitions induced by the vibrations of water molecules in an organic–inorganic hybrid halide (N-(2-ammoniumethyl)piperazinium) CuCl ₅ ·2H ₂ O Wang, Zhongxia; Lu, Yang; Zafar, Zainab Dalton Transactions, Vol. 46, Issue 31 https://doi.org/10.1039/c7dt01378g	journal	January 2017
Solvent-assisted ligand exchange (SALE) for the enhancement of epoxide ring-opening reaction catalysis based on three amide-functionalized metal–organic frameworks Gharib, Maniya; Esrafili, Leili; Morsali, Ali Dalton Transactions, Vol. 48, Issue 24 https://doi.org/10.1039/c9dt00941h	journal	January 2019
The right isotherms for the right reasons? Validation of generic force fields for prediction of methane adsorption in metal-organic frameworks Lennox, Matthew J.; Bound, Michelle; Henley, Alice Molecular Simulation, Vol. 43, Issue 10-11 https://doi.org/10.1080/08927022.2017.1301665	journal	March 2017
Fe(III) porphyrin metal–organic framework as an artificial enzyme mimics and its application in biosensing of glucose and H2O2 Dehghanpour, Saeed; Aghayan, Morvarid; Mahmoudi, Ali figshare https://doi.org/10.6084/m9.figshare.13726708	text	January 2021
Post-Synthetic Anisotropic Wet-Chemical Etching of Colloidal Sodalite ZIF Crystals Avci, Civan; Ariñez-Soriano, Javier; Carné-Sánchez, Arnau Angewandte Chemie, Vol. 127, Issue 48 https://doi.org/10.1002/ange.201507588	journal	October 2015
Cyclometalation of lanthanum( iii ) based MOF for catalytic hydrogenation of carbon dioxide to formate Tshuma, Piwai; Makhubela, Banothile C. E.; Öhrström, Lars RSC Advances, Vol. 10, Issue 6 https://doi.org/10.1039/c9ra09938g	journal	January 2020
Fe(III) porphyrin metal–organic framework as an artificial enzyme mimics and its application in biosensing of glucose and H2O2 Dehghanpour, Saeed; Aghayan, Morvarid; Mahmoudi, Ali figshare https://doi.org/10.6084/m9.figshare.13726708.v1	text	January 2021
Homo- and heterometallic complexes constructed from hexafluoroacetylacetonato and Schiff-base complexes as building-blocks Mocanu, Mihaela I.; Shova, Sergiu; Lloret, Francesc Taylor & Francis https://doi.org/10.6084/m9.figshare.5840577.v1	text	January 2018
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Influence of thermally induced structural transformations on the magnetic and luminescence properties of tartrate-based chiral lanthanide organic-frameworks Huizi-Rayo, Uxua; Zabala-Lekuona, Andoni; Terenzi, Alessio Journal of Materials Chemistry C, Vol. 8, Issue 24 https://doi.org/10.1039/d0tc00736f	journal	January 2020

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