Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal–organic frameworks

Marshall, Ross J.; Hobday, Claire L.; Murphie, Colin F.; Griffin, Sarah L.; Morrison, Carole A.; Moggach, Stephen A.; Forgan, Ross S.

doi:10.1039/c5ta10401g

Cited by 155 publications

(127 citation statements)

References 73 publications

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“…26,27 The kinetic inertness of the metal-oxygen bonds means that coordination modulationthe addition of competing monotopic ligands to syntheses -is commonplace to enhance their self-assembly and materials properties, but it is usually done so in a trial and error approach. [28][29][30] The modulating agent inuences the crystallisation kinetics, most likely by competing with the ligands for attachment to the metal clusters as they assemble in solution. Utilising modulators in MOF syntheses can result in the creation of defects, in the form of missing linkers and/or clusters with concomitant incorporation of capping modulators, which can impart the MOF with interesting and unusual physical properties.…”

Section: -16mentioning

confidence: 99%

“…However, low diffraction intensity and the slight differences observed for the high angle data led to attempts to improve crystallinity by modulating the synthesis of 1 (see ESI, Section S2 †) with the known modulators hydrochloric acid (one equivalent), 49 acetic acid (AA, thirty equivalents) 28 and L-proline (ve equivalents). 29 One equivalent each of scandium nitrate hydrate and bpdc-H 2 were combined in DMF, the modulator was added, and then the mixture was sonicated and heated at 120 C for 24…”

Section: Synthesis and Modulation Ofmentioning

confidence: 99%

“…Driven by our interest in the modulation of Zr MOFs 13,29,47 and the relatively limited research into Sc MOFs in comparison, we sought to extend modulated syntheses to Sc MOFs containing bpdc and bpydc ligands (Fig. 1b) in an attempt to: (i) conrm the structure and level of interpenetration of the reported Sc-bpdc MOF, 42 (ii) examine the extent of structural diversity, as seen for the Sc-bdc MOFs, in this series, and (iii) control the physical properties of the resulting materials.…”

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Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

et al. 2018

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Interpenetration in metal-organic frameworks (MOFs), where multiple nets of metal ions or clusters linked by organic ligands are nested within each other's pore spaces, affects important physical properties such as stability and gas uptake, and can be controlled through ligand sterics and modifying synthetic conditions. Herein, we extend the use of coordination modulation -deliberate addition of competing monotopic ligands to syntheses -to prepare Sc MOFs containing related biphenyl-4,4 0 -dicarboxylate (bpdc) and 2,2 0 -bipyridine-5,5 0 -dicarboxylate (bpydc) linkers. The Sc-bpdc MOF adopts a two-fold interpenetrated structure, however, the Sc-bpydc MOF is non-interpenetrated, despite only minor electronic modifications to the ligand. A comprehensive experimental and theoretical examination reveals that ligand twisting (energetically favourable for bpdc but not bpydc) and associated p-stacking interactions are a prerequisite for interpenetration. The more rigid Sc-bpdc is susceptible to modulation, resulting in differences in morphology, thermal stability and the synthesis of a highly defective, acetate-capped mesoporous material, while the large pore volume of Sc-bpydc allows postsynthetic metallation with CuCl 2 in a single-crystal to single-crystal manner. Controlling interpenetration through linker conformation could result in design of new materials with desirable properties such as bifunctional solidstate catalysts.

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Section: Synthesis and Modulation Ofmentioning

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Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

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“…This hypothesis was further supported by control experiments using an isostructural MOF with stable azobenzene-4,4'dicarboxylate (AZDC) as the linker. [13] No obvious Co-INA 2 incorporation was observed by SC-XRD after 2h.…”

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confidence: 94%

Sequential Transformation of Zirconium(IV)‐MOFs into Heterobimetallic MOFs Bearing Magnetic Anisotropic Cobalt(II) Centers

Yuan

Qin

et al. 2018

Angewandte Chemie

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Heterometallic metal-organic frameworks (MOFs) allowt he precise placement of various metals at atomic precision within aporous framework. This new level of control by MOFs promises fascinating advances in basic science and application. However,t he rational design and synthesis of heterometallic MOFs remains achallenge due to the complexity of the heterometallic systems.H erein, we showt hat bimetallic MOFs with MX 2 (INA) 4 moieties (INA = isonicotinate;M= Co 2+ or Fe 2+ ;X = OH À ,C l À ,B r À ,I À ,N CS À ,o r NCSe À )c an be generated by the sequential modification of aZ r-based MOF.T his multi-step modification not only replaced the linear organic linker with as quare planar MX 2 (INA) 4 unit, but also altered the symmetry,u nit cell, and topology of the parent structure.Single-crystal to single-crystal transformation is realized so that snapshots for transition process were captured by successive single-crystal X-ray diffraction. Furthermore,t he installation of Co(NCS) 2 (INA) 4 endows field-induced slow magnetic relaxation property to the diamagnetic Zr-MOF.

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“…Addition of competing ligands to MOF synthesis is commonly known as coordination modulation, 89 and has been applied both to downsizing MOF crystal size [90][91][92] and also to enhancing the syntheses of MOFs linked by early transition metals such as zirconium. 93,94 Solvothermal reaction of (TBA) 80 It is clear that hybrid POMS can assemble into a diverse range of complex coordination polymer structures, and we expect these synthetic guidelines will assist in future efforts to control the self-assembly of hybrid polyoxometalates into extended porous networks and enhance the reproducibility of their syntheses.…”

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Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

Yazigi

Wilson

Long

et al. 2017

Crystal Growth & Design

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The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal-organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilised, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups towards linking metal cations leading to a diverse range of structures, but incorporation of organic donor units into hybrid POMs offers an alternative methodology to programmably synthesise POM/MOF conjugates. Herein, we report six coordination polymers obtained serendipitously wherein Zn 2+ and Cu 2+ link pyridine-appended Mn-Anderson clusters into two-and three-dimensional network solids with complex connectivities and topologies.2 Careful inspection of their solid-state structures has allowed us to identify common structuredirecting features across these coordination polymers, including a square motif where two Zn 2+ cations bridge two POMs. By correlating certain structural motifs with synthetic conditions we have formulated a series of design considerations for the self-assembly of coordination polymers of hybrid POMs, encompassing the selection of reaction conditions, co-ligands and linking metal cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid POMs into functional MOF materials. INTRODUCTIONPolyoxometalates ( ) that have been widely studied for their catalytic, [4][5][6][7][8][9] magnetic, 10-17 photochromic 18-21 and redox properties. [22][23][24][25][26][27][28] Given their large range of their chemical and physical properties, their incorporation into Metal-Organic Frameworks (MOFs) -network structures composed of metal clusters or metal ions connected by organic linkers -or more generally into porous frameworks has been investigated. 29,30 Creating POM/MOF conjugate materials can associate their individual properties, for instance the catalytic properties of a POM with the large surface area of a MOF, 31 or achieving a synergistic effect, for example the cooperative effect of single molecule magnets 32 or enhanced photocatalytic proton reduction. 33 To do so, two main approaches have been followed to date ( Figure 1a). The first is the impregnation of the POMs into the pores of a MOF, where POMs are either added during the MOF synthesis and trapped in the pores, [34][35][36][37][38][39][40] or they are inserted postsynthetically by soaking the MOF in a solution of the desired POM. [41][42][43][44] The second approach is to consider POMs as building blocks for porous structures, 45 with the aim of creating a bond between the POM and 3 either an organic linker (usually a multitopic carboxylic acid or N-donor ligand) [46][47][48][49] -di-(4-pyridyl)-1,4,5,8- (Figures 1b and 1c). The amido-pyridyl tris-alkoxo MnAnderson (POM-1) has been reported previously 76 and sh...

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Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal–organic frameworks

Abstract: Addition of small quantities of amino acids to solvothermal and microwave syntheses of Zr and Hf MOFs drastically improves their crystallinity to the extent that single crystal structures can be obtained.

Cited by 155 publications

References 73 publications

Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

Sequential Transformation of Zirconium(IV)‐MOFs into Heterobimetallic MOFs Bearing Magnetic Anisotropic Cobalt(II) Centers

Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

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