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Cyclic Aliphatic Hydrocarbons As Linkers in Metal‐Organic

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Cyclic Aliphatic Hydrocarbons As Linkers in Metal‐Organic CORE Metadata, citation and similar papers at core.ac.uk Provided by Keele Research Repository Minireviews ChemPlusChem doi.org/10.1002/cplu.202000206 1 2 3 Cyclic Aliphatic Hydrocarbons as Linkers in Metal-Organic 4 5 Frameworks: New Frontiers for Ligand Design 6 [a] [b] [a] 7 Valentyna D. Slyusarchuk, Paul E. Kruger, and Chris S. Hawes* 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 ChemPlusChem 2020, 85, 845–854 845 © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley VCH Donnerstag, 07.05.2020 2005 / 165611 [S. 845/854] 1 Minireviews ChemPlusChem doi.org/10.1002/cplu.202000206 1 In this Minireview we outline the development of cyclic ties which are unattainable from conventional ligands. Here, we 2 aliphatic moieties as ligands in metal-organic frameworks focus on rigid and semi-rigid backbone moieties derived from 3 (MOFs), with a focus on the relationship between ligand design monocyclic and fused polycyclic aliphatic backbones, including 4 and synthesis and the properties of the subsequent materials. cyclohexane and adamantane, cubane and bicyclo[2.2.2]octane, 5 Aliphatic ligands have received considerably less attention than and discuss the synthetic chemistry of these species along with 6 aromatic analogues in MOF chemistry but offer advantages in their potential importance as the next generation of building 7 their unique combinations of geometric and electronic proper- blocks for microporous materials. 8 9 Introduction however, is the dominance of aromatic ligands in MOF 10 chemistry, with some commonly encountered examples shown 11 The study of Metal-Organic Frameworks (MOFs) encompasses in Figure 1.[13] Ignoring the simpler bridging ligands such as 12 all aspects of modern chemistry. From their beginnings as formate, oxalate and cyanide, and bridging oxides or fluori- 13 structural analogues of inorganic materials and the early studies nated anions, it becomes abundantly clear that non-aromatic 14 into their potential for hydrogen storage,[1] MOFs have grown ligands are an under-represented class of building blocks. 15 into platforms for interdisciplinary study from all branches of There are several explanations for the dominance of 16 chemistry. This is largely due to their modularity: with modern aromatic ligands in MOF chemistry. Rigid aromatic linkers lend 17 synthetic methods, essentially any known property of organic structural stability to open framework compounds,[14] and 18 or inorganic materials can be incorporated into the porous and polycyclic aromatic ligands can be generally prepared easily 19 monodisperse frameworks of these materials.[2] While many through standard metal-catalyzed coupling reactions. Aromatic 20 studies remain focused on gas adsorption and separation,[3] ligands also offer useful electronic properties, with their 21 catalysis,[4] magnetism[5] and sensing,[6] the modern MOF field is extended π-surfaces being implicated as sites for CO 22 2 also host to a plethora of much more niche applications.[7] In all adsorption,[15] or lending beneficial energy transfer mechanisms 23 cases, the combination of tunable metal/ligand character, for photochemistry.[16] Aliphatic ligands on the other hand, tend 24 precise control of microporosity, well-defined host-guest to suffer from poor structural stability due to the much greater 25 chemistry and advanced characterization methods have proven conformational freedom when present as linear alkanes,[17] and 26 irresistible. rigid or polycyclic alkanes are typically much more challenging 27 As the field moves towards a more applications-focused to prepare with suitable functional groups for metal coordina- 28 regime, a vital aspect of MOF chemistry which remains tion. Nonetheless, ligands with partially or entirely non-aromatic 29 prevalent is the necessity of effective ligand design.[8] In backbones, such as those represented in Figure 2, have much 30 Robson’s seminal report describing the deliberate pursuit of a to offer as unique building blocks within MOFs. Cyclic aliphatic 31 porous coordination polymer with a specific targeted topology, species especially can mimic the levels of rigidity observed in 32 the design and synthesis of an appropriate organic ligand was aromatic species, but with additional, unique benefits: 33 essential.[9] In that case, the ligand 4,4',4'',4'''-tetracyanotetra- 1) 3-dimensional structures: as non-planar scaffolds, cyclic or 34 phenylmethane was correctly predicted as an extended tetrahe- polycyclic species offer access to useful and unusual node 35 dral linker to realize a porous diamondoid topology. Since then, geometries. This approach has already been widely and 36 thousands of MOFs (some designed, some serendipitous) have successfully adopted in the preparation of microporous 37 emerged with an abundance of ligand functionalities.[10] How- organic polymers.[18] 38 ever, the rate of expansion of the field has outstripped the 2) Non-polar backbones: introducing aliphatic character into 39 supply of new ligand classes, and most reported MOFs today pore walls has long been suggested as a mechanism for 40 make use of only a relatively small group of ligand families.[11] improving hydrophobicity in water-sensitive MOFs.[19] 41 Carboxylates remain the most popular coordinating group by a 42 significant margin, followed by pyridines, cyanides and imida- 43 zoles, pyrazoles, triazoles and tetrazoles, as more exotic donor 44 groups appear less frequently.[12] Even more pronounced, 45 46 [a] V. D. Slyusarchuk, Dr. C. S. Hawes 47 School of Chemical and Physical Sciences 48 Keele University 49 Keele ST5 5BG (United Kingdom) E-mail: [email protected] 50 [b] Prof. P. E. Kruger 51 MacDiarmid Institute for Advanced Materials and Nanotechnology 52 School of Physical and Chemical Sciences 53 University of Canterbury Christchurch 8140 (New Zealand) 54 This article is part of a Special Collection on “Supramolecular Chemistry: 55 Young Talents and their Mentors”. More articles can be found under https:// Figure 1. The 10 most common linkers in the CoRE MOF 2019-ASR subset.[13] 56 onlinelibrary.wiley.com/doi/toc/10.1002/(ISSN)2192-6506.Supramolecular- Chemistry. Carboxylic acids are represented in their protonated forms for simplicity. 57 ChemPlusChem 2020, 85, 845–854 www.chempluschem.org 846 © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley VCH Donnerstag, 07.05.2020 2005 / 165611 [S. 846/854] 1 Minireviews ChemPlusChem doi.org/10.1002/cplu.202000206 potential MOF applications, both in providing new routes to 1 ligand-based functionality and in the ever-expanding field of 2 MOF catalysis as a testbed for new reactivity.[24] Likewise, the 3 growth of MOF chemistry as a discipline provides new 4 challenges for synthetic chemistry, both in the laboratory and, 5 in the future, at the process scale. 6 In this minireview, we outline the origins and recent 7 progress that has been made in cyclic aliphatic ligand design, 8 and the relationship that exists between the design and 9 synthesis of new aliphatic ligands and the structure and 10 Figure 2. Structures of the cyclic and polycyclic aliphatic cores of interest to function of the resulting MOFs. 11 this review. 12 13 Results and Discussion 14 Although grafting alkyl chains to aromatic linkers is one 15 method of achieving this outcome, doing so comes at a cost Monocyclic backbones 16 to pore volume.[20] 17 3) Fluxional behavior: Unlike their linear alkane counterparts, The use of commercially available aliphatic or olefinic dicarbox- 18 where multiple conformations are freely accessible by low- ylates in MOF chemistry has been widespread, with commer- 19 energy bond rotations, the conformational isomerism of cially available malonate, fumarate, adipate, succinate and other 20 cycloalkanes or azacycles gives very distinct ligand geo- linear alkanes or alkene linkers accounting for many of the 21 metries separated by relatively large (>30 kJmolÀ 1) energy reported examples.[25] Cyclohexane carboxylates have been the 22 barriers.[21] In instances where multiple stable conformers most widely studied cyclic aliphatic ligands, with between two 23 can be accessed, this provides a pool of multiple ligand and six carboxylic acid groups varying in both position and 24 geometries in solution which can lead to fascinating relative stereochemistry.[26] Generally, these species are com- 25 structural outcomes (provided the resulting MOFs can retain mercially available and examples of ligand syntheses for 26 their structural stability).[22] cyclohexyl-cored MOF ligands are rare and mostly involve 27 In pursuing these outcomes, the role of organic synthesis peripheral substitution.[27] 28 cannot be overlooked. While MOFs derived from commercially The issue of relative stereochemistry in cyclohexane deriva- 29 available ligands have obvious practical advantages, some of tives has provided interesting opportunities for structural 30 the most important and memorable breakthroughs in MOF engineering in MOFs. Cyclohexane-1,2,4,5-tetracarboxylic acid, 31 chemistry in the last two decades have required bespoke ligand for example, is commercially available and can be found as a 32 design and synthesis.[23] Contemporary advances in synthetic mixture of up to four non-equivalent isomers. Tong and co- 33 methods have been instrumental in expanding the scope of workers, using a recrystallized source of the mutually cis, meso- 34 35 36 Valentyna Slyusarchuk completed her under- Chris Hawes completed his PhD at the Uni- 37 graduate degree in Environmental and Sus- versity of Canterbury, New Zealand under the 38 tainable Chemistry at University College Dub- supervision of Prof. Paul Kruger in 2012. He 39 lin, Ireland, and studied magneto-structural subsequently went on to postdoctoral posi- 40 correlations in copper carbonate chains under tions at Monash University, Australia and the supervision of Asst. Prof. Tony Keene. She Trinity College Dublin, Ireland. He was ap- 41 began her PhD at Keele University under the pointed as a Lecturer at Keele University, U.K.
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