Co-reporter:Stephen D. Worrall, Haydn Mann, Adam Rogers, Mark A. Bissett, Martin P. Attfield, Robert A.W. Dryfe
Electrochimica Acta 2016 Volume 197() pp:228-240
Publication Date(Web):10 April 2016
DOI:10.1016/j.electacta.2016.02.145
•ZIF-4, -7, -8, -14 and -67 electrode coatings obtained via anodic dissolution.•Reaction conditions optimised to favour coating formation.•Capacitance of 10.45 mF cm−2 for ZIF-67, highest for additive free MOF.Zn and Co electrodes have been successfully coated with five different zeolitic imidazolate frameworks ZIFs (ZIF-4, ZIF-7, ZIF-8, ZIF-14 and ZIF-67) via the anodic dissolution method. Careful control of the reaction conditions allows for electrode coating growth; in contrast to previous reports of electrochemical ZIF growth, which have not succeeded in obtaining ZIF electrode coatings. Coating crystallinity is also shown to be heavily dependent upon reaction conditions, with amorphous rather than crystalline material generated at shorter reaction times and lower linker concentrations. Electrochemical applications for ZIF-coated electrodes are highlighted with the observation of an areal capacitance of 10.45 mF cm−2 at 0.01 V s−1 for additive-free ZIF-67 coated Co electrodes. This is superior to many reported metal organic framework (MOF)/graphene composites and to capacitance values previously reported for additive-free MOFs.Figure optionsDownload full-size imageDownload high-quality image (119 K)Download as PowerPoint slide
Co-reporter:M. P. Attfield, M. Feygenson, J. C. Neuefeind, T. E. Proffen, T. C. A. Lucas and J. A. Hriljac
RSC Advances 2016 vol. 6(Issue 24) pp:19903-19909
Publication Date(Web):11 Feb 2016
DOI:10.1039/C5RA23827G
A combination of Rietveld refinement and pair distribution function analysis of total neutron scattering data are used to provide insight into the negative thermal expansion mechanism of siliceous faujasite. The negative thermal expansion mechanism of siliceous faujasite is attributed to the transverse vibrations of bridging oxygen atoms resulting in the coupled librations of the SiO4 tetrahedra. The constituent SiO4 tetrahedra are revealed to expand in size with temperature and they are also shown to undergo some distortion as temperature is increased. However, these distortions are not distinct enough in any geometric manner for the average behaviour of the SiO4 tetrahedra not to be considered as that of a rigid units. The work displays the benefits of using total scattering experiments to unveil the finer details of dynamic thermomechanical processes within crystalline materials.
Co-reporter:Chompoonoot Nanthamathee, Sanliang Ling, Ben Slater, and Martin P. Attfield
Chemistry of Materials 2015 Volume 27(Issue 1) pp:85
Publication Date(Web):December 10, 2014
DOI:10.1021/cm503311x
The influence of simple framework inorganic anions on the thermoresponsive behavior of the isostructural MIL-53 type metal–organic frameworks [AlF(bdc)] and [Al(OH)(bdc)] has been determined using a combination of diffraction and computational techniques. [AlF(bdc)] has an orthorhombic large pore structure from 500 to ∼175 K at which point it undergoes a subtle distortion to form a monoclinic large pore structure that remains stable to 11 K. The orthorhombic large pore form of [AlF(bdc)] exhibits negative thermal expansion from 175–500 K. [Al(OH)(bdc)] has an orthorhombic large pore structure from 500 to 125 K at which point it undergoes a displacive phase transition, a breathing effect, to form a nonporous monoclinic structure. The orthorhombic large pore form of [Al(OH)(bdc)] exhibits positive thermal expansion from 150 to 500 K. The presence of a breathing effect in [Al(OH)(bdc)], and not [AlF(bdc)], is related to the additional contributions to attractive interactions across the shortest dimension of the pore provided by the presence of the hydroxide groups. The display of positive or negative thermal expansion of the orthorhombic large pore structure of either material is related to the rigidity of the constituent corner-sharing chain of AlO4X2 octahedra with the more rigid AlO4F2 octahedra favoring one type of static or dynamic displacement and the less rigid AlO4(OH)2 octahedra favoring a different type of static displacement. Formation of metal–organic frameworks with controlled expansion and displacive phase transition properties, or simultaneously containing mixed thermoresponsive properties, is predicted through control of the identity and amount of the simple inorganic anions in this family of material. The work indicates the importance of considering the simplest species when designing the thermo-mechanical properties of metal–organic frameworks.
Co-reporter:Pablo Cubillas, Kimberley Etherington, Michael W. Anderson and Martin P. Attfield
CrystEngComm 2014 vol. 16(Issue 42) pp:9834-9841
Publication Date(Web):11 Sep 2014
DOI:10.1039/C4CE01710B
Crystal growth of the metal–organic framework, MOF-5, using basic zinc benzoate, [Zn4O(O2CC6H5)6], was studied in real time using atomic force microscopy. The two-dimensional nuclei involved in layer growth were found to form by a two-step process whereby 1,4-benzenedicarboxylate units first attach to the MOF-5 surface followed by addition of a layer of Zn species and connecting 1,4-benzenedicarboxylate units. No evidence of a growth mechanism involving nucleophilic substitution of a benzoate group from an intact [Zn4O(O2CC6H5)6] molecule by a surface attached 1,4-benzenedicarboxylate unit was found. This indicates that the [Zn4O(O2CC6H5)6] molecules undergo a degree of dissociation before incorporation into the MOF-5 framework. The [Zn4O(O2CC6H5)6]-containing growth solutions were found to influence the relative growth rates along different crystallographic directions and to lead to a faster nucleation rate under certain conditions when compared to growth solutions containing simpler zinc salts. This suggests a degree of remnant association of the zinc species derived from the [Zn4O(O2CC6H5)6] cluster during crystal growth under these conditions.
Co-reporter:Pablo Cubillas, Michael W. Anderson, and Martin P. Attfield
Crystal Growth & Design 2013 Volume 13(Issue 10) pp:4526-4532
Publication Date(Web):August 23, 2013
DOI:10.1021/cg401001f
Atomic force microscopy is used to conduct the first detailed nanoscopic study on the crystal growth of a complex mixed metal/metal–organic framework based on the MOF-5 framework topology. Shells of isomorphously substituted Co/Zn-MOF-5 and MOF-5 were epitaxially grown on MOF-5 core crystals at room temperature and low supersaturation to produce complex core–shell–shell structures with a hierarchal mixed metal nature involving mixing at the atomic level in the isomorphously substituted Co/Zn-MOF-5 shell and at the nanometer level through segregation of the Co/Zn-MOF-5 and MOF-5 layers. The presence of cobalt in the growth solutions was found to retard the overall rate of surface growth in comparison to a cobalt-free growth solution and stop growth entirely for a growth solution containing a Zn/Co ratio = 0.6. The presence of cobalt in the growth solutions was also found to affect the relative rates of terrace spreading in different crystallographic directions compared to cobalt-free growth with spreading in the ⟨110⟩ directions decreasing relative to the rate along the ⟨100⟩ directions. The work provides new understanding of the crystal growth of complex mixed metal/metal–organic frameworks and a methodology to prepare these complex forms in a more controlled manner.
Co-reporter:Pak Y. Moh, Magdalena Brenda, Michael W. Anderson and Martin P. Attfield
CrystEngComm 2013 vol. 15(Issue 45) pp:9672-9678
Publication Date(Web):13 Aug 2013
DOI:10.1039/C3CE40943K
A gravimetric study of the solvothermal dimethylformamide-mediated crystallisation of the metal–organic framework ZIF-8 has enabled the rate constants and activation energies of the nucleation and crystal growth processes to be determined. The kinetics analyses reveal the crystallisation is nucleation controlled with activation energies for nucleation and crystal growth of 115.1 and 87.7 kJ mol−1, respectively. The results are compared to the crystallisation kinetics for other syntheses of ZIF-8 and other MOFs to reveal the importance that different solvents, different metal ion/organic linker ratios and the presence of deprotonating modulators have on these processes. Temporal ex situ monitoring of the crystal morphology and surface topography during crystallisation reveals the crystals evolve to the equilibrium rhombic dodecahedral morphology via edge-truncated cubic and corner-truncated rhombic dodecahedral habits while relatively smooth surfaces containing large truncated rhombic surface terraces and growth spirals develop through rough surfaces consisting of numerous ill-defined small growth islands and steps. The combination of techniques applied over different size scales provides important understanding for potential control over the crystal properties of MOFs for new application or enhanced performance in current applications.
Co-reporter:Dr. Pablo Cubillas; Michael W. Anderson ;Dr. Martin P. Attfield
Chemistry - A European Journal 2013 Volume 19( Issue 25) pp:8236-8243
Publication Date(Web):
DOI:10.1002/chem.201300778
Abstract
A new zeolitic–imidazolate framework (ZIF), [Zn(imidazolate)2−x(benzimidazolate)x], that has the zeolite A (LTA) framework topology and contains relatively inexpensive organic linkers has been revealed using in situ atomic force microscopy. The new material was grown on the structure-directing surface of [Zn(imidazolate)1.5(5-chlorobenzimidazolate)0.5] (ZIF-76) crystals, a metal–organic framework (MOF) that also possesses the LTA framework topology. The crystal growth processes for both [Zn(imidazolate)2−x(benzimidazolate)x] and ZIF-76 were observed using in situ atomic force microscopy; it is the first time the growth process of a nanoporous material with the complex zeolite A (LTA) framework topology has been monitored temporally at the nanoscale. The results reveal the crystal growth mechanisms and possible surface terminations on the {100} and {111} facets of the materials under low supersaturation conditions. Surface growth of these structurally complex materials was found to proceed through both “birth-and-spread” and spiral crystal-growth mechanisms, with the former occurring through the nucleation and spreading of metastable and stable sub-layers reliant on the presence of non-framework species to bridge the framework during formation. These results support the notion that the latter process may be a general mechanism of surface crystal growth applicable to numerous crystalline nanoporous materials of differing complexity and demonstrate that the methodology of seeded crystal growth can be used to discover previously unobtainable ZIFs and MOFs with desirable framework compositions.
Co-reporter:Martin P. Attfield and Pablo Cubillas
Dalton Transactions 2012 vol. 41(Issue 14) pp:3869-3878
Publication Date(Web):19 Dec 2011
DOI:10.1039/C2DT12006B
Nanoporous metal organic frameworks (MOFs) form one of the newest families of crystalline nanoporous material that is receiving worldwide attention. Successful use of MOFs for application requires not only development of new materials but also a need to control their crystal properties such as size, morphology, and defect concentration. An understanding of the crystal growth processes is necessary in order to aid development of routes to control such properties of the crystallites. In this Perspective article we aim to provide a short overview of the current work and understanding concerning the nucleation and growth processes of nanoporous MOFs and how this work may be expanded upon to further our comprehension of this subject. We also focus heavily on in situ studies that provide real time information on the developing materials and generally provide the most conclusive findings on the processes under investigation.
Co-reporter:Martin P. Attfield, Carlos Mendieta-Tan, Ryan N. Telchadder and Mark A. Roberts
RSC Advances 2012 vol. 2(Issue 27) pp:10291-10297
Publication Date(Web):31 Aug 2012
DOI:10.1039/C2RA21930A
We report here the hydrothermal synthesis, crystal structure and properties of the hybrid inorganic–organic framework material Al2[O3PC6H4PO3](H2O)2F2·2H2O which is the seventh member of the group 13 metal diphosphonate framework series of formula M(III)2[O3PRPO3](H2O)2F2. The structure is formed from linear chains of corner-sharing AlO4F2 octahedra in which the two fluorine atoms are present in a trans configuration. The diphosphonate groups link the chains together through Al–O–P–O–Al bridges and through the phenylene groups to form a three-dimensional framework structure containing a one-dimensional channel system containing eight non-framework water molecules per unit cell. The framework structure remains crystalline with respect to the loss of the non-framework water molecules but removal of the framework water molecules results in a rapid loss of framework stability and crystallinity. The work demonstrates the potential to design the structure and void volume of a hybrid framework material through directed formation of the extended two-dimensional inorganic component and the packing of the organic component within the interlayer region.
Co-reporter:Dr. Pablo Cubillas; Michael W. Anderson ;Dr. Martin P. Attfield
Chemistry - A European Journal 2012 Volume 18( Issue 48) pp:15406-15415
Publication Date(Web):
DOI:10.1002/chem.201202261
Abstract
Crystal growth of the metal–organic framework MOF-5 was studied by atomic force microscopy (AFM) for the first time. Growth under low supersaturation conditions was found to occur by a two-dimensional or spiral crystal growth mechanism. Observation of developing nuclei during the former reveals growth occurs through a process of nucleation and spreading of metastable and stable sub-layers revealing that MOFs may be considered as dense phase structures in terms of crystal growth, even though they contain sub-layers consisting of ordered framework and disordered non-framework components. These results also support the notion this may be a general mechanism of surface crystal growth at low supersaturation applicable to crystalline nanoporous materials. The crystal growth mechanism at the atomistic level was also seen to vary as a function of the growth solution Zn/H2bdc ratio producing square terraces with steps parallel to the <100> direction or rhombus-shaped terraces with steps parallel to the <110> direction when the Zn/H2bdc ratio was >1 or about 1, respectively. The change in relative growth rates can be explained in terms of changes in the solution species concentrations and their influence on growth at different terrace growth sites. These results were successfully applied to the growth of as-synthesized cube-shaped crystals to increase expression of the {111} faces and to grow octahedral crystals of suitable quality to image using AFM. This modulator-free route to control the crystal morphology of MOF-5 crystals should be applicable to a wide variety of MOFs to achieve the desired morphological control for performance enhancement in applications.
Co-reporter:Pak Y. Moh ; Pablo Cubillas ; Michael W. Anderson
Journal of the American Chemical Society 2011 Volume 133(Issue 34) pp:13304-13307
Publication Date(Web):August 5, 2011
DOI:10.1021/ja205900f
Crystalline nanoporous materials are one of the most important families of complex functional material. Many questions pertaining to the molecular assembly mechanism of the framework of these materials remain unanswered. Only recently has it become possible to answer definitively some of these questions by observation of growing nanoscopic surface features on metal organic frameworks (MOFs) through use of in situ atomic force microscopy (AFM). Here we reveal that a growth process of a MOF, zeolitic imidazolate framework ZIF-8, occurs through the nucleation and spreading of successive metastable unenclosed substeps to eventually form stable surface steps of the enclosed framework structure and that this process is reliant on the presence of nonframework species to bridge the developing pores during growth. The experiments also enable identification of some of the fundamental units in the growth process and the stable crystal surface plane. The former findings will be applicable to numerous nanoporous materials and support efforts to synthesize and design new frameworks and to control the crystal properties of these materials.
Co-reporter:Martin P. Attfield, Yousef Al-Ebini and Patrick Hill
Journal of Materials Chemistry A 2010 vol. 20(Issue 39) pp:8686-8692
Publication Date(Web):07 Sep 2010
DOI:10.1039/C0JM01429J
The core/shell composite silicogermanate zeotype material, Si-ASU-7, has been prepared in a one-step solvothermal synthesis process from a reactant mixture of GeO2 and SiO2 in a dimethylamine/H2O/HF solvent mixture. The core/shell nature of the product material has been determined using a combination of X-ray diffraction on powder and single crystal samples, and energy dispersive X-ray spectroscopy. The crystal structure of Si-ASU-7, ([Si0.221Ge0.779O2]10·(Me2NH)(H2O), tetragonal, space group P4/mnc, a = 12.3484(3) Å, c = 14.3979(5) Å, V = 2195.43(11) Å3) determined using single crystal X-ray diffraction data indicates that incorporation of silicon into the structure introduces a degree of disorder to the orientation of the double 4-ring secondary building units from which the framework is constructed. The thermal stability of the as-synthesised composite Si-ASU-7 material is enhanced compared to the pure germanate material ASU-7.
Co-reporter:Martin P. Attfield ; Zhanhui Yuan ; Howard G. Harvey ;William Clegg
Inorganic Chemistry 2010 Volume 49(Issue 6) pp:2656-2666
Publication Date(Web):February 18, 2010
DOI:10.1021/ic901651d
Three new gallium diphosphonates: Ga3(OH)(O3PC3H6PO3)2 (1), Ga4(O3PC5H10PO3)3(C5H5N)2 (2), and Ga(HO3PC10H20PO3) (3), in which the diphosphonate bridging ligands have 3, 5, and 10 methylene units, respectively, have been synthesized using solvothermal methods and their structures determined using single-crystal laboratory and synchrotron X-ray diffraction data. All three materials contain Ga-centered tetrahedra and octahedra linked together through the −PO3 groups of the diphosphonate ligands to form two-dimensional pillared slab (1) and three-dimensional pillared (2 and 3) materials. Compound 1 contains bridging hydroxide anions that connect Ga-centered octahedra and tetrahedra, and contains pillared slabs in which one side of the Ga−P−O/OH/CH hybrid layers are connected by the propylenediphosphonate groups only. This slab also contains propylenediphosphonate groups arranged orthogonally to the pillaring direction in the outermost layer of the Ga−P−O/OH/CH hybrid layers. Compound 2 is a framework structure that contains framework pyridine molecules between alternate layers of diphosphonate-pillared Ga−P−O layers and is structurally stable to loss of 1 equiv of pyridine molecules from the structure. Compound 3 is a partially condensed pillared framework structure with one P−O−H bond per diphosphonate group remaining in the resulting material. The structural changes observed as the alkylene chain in the diphosphonate ligand is increased in these compounds is compared to other members of the gallium diphosphonate family synthesized in a similar manner, and other metal diphosphonate series, to gain some general oversight of the structural trends observed in series of metal diphosphonate materials in which the alkylene chain length is varied systematically.
Co-reporter:Neena S. John, Camilla Scherb, Maryiam Shöâeè, Michael W. Anderson, Martin P. Attfield and Thomas Bein
Chemical Communications 2009 (Issue 41) pp:6294-6296
Publication Date(Web):07 Sep 2009
DOI:10.1039/B908299A
In situ
atomic force microscopy was used to directly investigate the growth processes of the oriented metal–organic framework HKUST-1 grown on self-assembled monolayers on gold.
Co-reporter:Martin P. Attfield, Faisal Al-Otaibi, Yousef Al-Ebini
Microporous and Mesoporous Materials 2009 Volume 118(1–3) pp:508-512
Publication Date(Web):1 February 2009
DOI:10.1016/j.micromeso.2008.08.052
The structure of the germanate zeotype material ASU-7 has been redetermined (tetragonal, space group P4/mnc, a = 12.4222(5) Å c = 14.4815(3) Å, V = 2234.66(14) Å3, R1 = 0.0289 and wR2 = 0.0762 for 867 (I > 2σ(I)) reflections) and shown to possess an ordered framework with a regular arrangement of the constituent double four ring units. The regular arrangement of the constituent rectangular prism-shaped double four ring units results in two, subtly different, 12-membered rings channels being defined along the crystallographic c-axis.
Co-reporter:Zhanhui Yuan, William Clegg, Martin P. Attfield
Journal of Solid State Chemistry 2009 Volume 182(Issue 11) pp:3049-3054
Publication Date(Web):November 2009
DOI:10.1016/j.jssc.2009.08.021
The novel aluminum ethylenediphosphonate fluoride, [HN(CH2CH2NH3)3][Al2(O3PCH2CH2PO3)2F2]·H2O (1) (monoclinic, P21/n, a=12.145(4) Å, b=9.265(3) Å, c=20.422(6) Å, β=104.952(4)°, Z=3, R1=0.092, wR2=0.196) has been synthesized by solvothermal methods in the presence of tris(2-aminoethyl)amine and its structure determined using single microcrystal X-ray diffraction data. Compound 1 is a one-dimensional extended chain structure composed of well-separated anionic [Al2(O3PCH2CH2PO3)2F2]4− rods containing helical chains of corner-shared cis-AlO4F2 octahedra at their core. The charge-compensating tris(2-aminoethyl)ammonium cations separate the anionic [Al2(O3PCH2CH2PO3)2F2]4− rods that contain either left- or right-handed helical chains. The incorporation of the organic components into this hybrid material has aided the adoption of one-dimensionality by the compound and defined the pitch of the helical AlO4F chain.Helical chains of corner-shared cis-AlO4F2 octahedra form the core of well-separated anionic [Al2(O3PCH2CH2PO3)2F2]4− rods in the novel hybrid aluminum diphosphonate material, (H4tren)[Al2(O3PCH2CH2PO3)2F2]·(H2O). The incorporation of the organic components into this hybrid material has aided the adoption of a uni-dimensional structure and a specific structural aspect, the helical pitch, within the resulting material, which indicates the potential of this approach to form particular structural features within hybrid materials.
Co-reporter:Martin P. Attfield, Carlos Mendieta-Tan, Zhanhui Yuan, William Clegg
Solid State Sciences 2008 Volume 10(Issue 9) pp:1124-1131
Publication Date(Web):September 2008
DOI:10.1016/j.solidstatesciences.2007.12.014
A combination of techniques has been used to fully determine the structure and properties of Al2[O3PC4H8PO3](H2O)2F2·2H2O (monoclinic, P21/m, a = 4.96926(6) Å, b = 12.0013(1) Å, c = 10.7440(2) Å, β = 94.058(1)°, Z = 2, Rp = 0.0732, Rwp = 0.0939), the n = 4 member of the framework aluminium alkylenediphosphonate Al2[O3PCnH2nPO3](H2O)2F2 series. The combination of thermogravimetric and thermodiffraction data and the structure determination of the partially dehydrated structure, Al2[O3PC4H8PO3](H2O)2F2·0.17(1)H2O (monoclinic, P21/m, a = 4.9392(3) Å, b = 12.1867(4) Å, c = 10.7830(5) Å, β = 94.767(3)°, Z = 2, Rp = 0.0839, Rwp = 0.1121), indicate that the framework structure is stable to, and remains unchanged, with respect to the loss of the extra-framework water molecules but not the framework water molecules. This behaviour is in stark contrast to the n = 3 member of the Al2[O3PCnH2nPO3](H2O)2F2 series, Al2[O3PC3H6PO3](H2O)2F2·H2O, for which the combination of thermogravimetric and thermodiffraction data indicates that the framework structure contracts during the loss of the extra-framework water molecules before collapsing after loss of the framework water molecules. The formation of the n = 4 member of the series indicates that the design of the alkyl chain can be used to successfully control aspects of the pore volume within this family of materials and comparison of the dehydration behaviour of the n = 3 and n = 4 members of the series indicates that related materials containing channels housing the same number of water molecules exhibit different dehydration behaviour depending on the stacking of the constituent inorganic layers within the material.
Co-reporter:Maryiam Shoaee;MichaelW. Anderson ;MartinP. Attfield Dr.
Angewandte Chemie International Edition 2008 Volume 47( Issue 44) pp:8525-8528
Publication Date(Web):
DOI:10.1002/anie.200803460
Co-reporter:Maryiam Shoaee;MichaelW. Anderson ;MartinP. Attfield Dr.
Angewandte Chemie 2008 Volume 120( Issue 44) pp:8653-8656
Publication Date(Web):
DOI:10.1002/ange.200803460
Co-reporter:Howard G. Harvey, Martin P. Attfield
Solid State Sciences 2006 Volume 8(3–4) pp:404-412
Publication Date(Web):March–April 2006
DOI:10.1016/j.solidstatesciences.2006.02.019
The new aluminum diphosphonate, (C5H5NH){AlF[O3PCH2PO2(OH)]}⋅0.61H2O (monoclinic, C2/cC2/c, a=18.1898(11) Åa=18.1898(11) Å, b=10.7396(7) Åb=10.7396(7) Å, c=12.0022(7) Åc=12.0022(7) Å, β=105.404(2)°β=105.404(2)°, V=2260.4(2) Å3V=2260.4(2) Å3, Z=8Z=8), has been synthesized by solvothermal methods and its structure determined using micro-crystal X-ray diffraction data. The material consists of infinite columnar [AlF(O3PCH2PO3)]2−∞ anions with chains of cis- and trans- vertex-sharing AlO4F2 octahedra at their core. Each methylenediphosphonate group acts as a bisbidentate ligand bonding to adjacent aluminum atoms in a chain, and directly binding to one chain only. The columnar [AlF(O3PCH2PO3)]2−∞ anions are connected together through hydrogen-bonding interactions to form a hydrogen-bonded framework material containing pyridinium cations and extra-framework water molecules within its channels.
Co-reporter:Zhanhui Yuan, William Clegg, Martin P. Attfield
Journal of Solid State Chemistry 2006 Volume 179(Issue 6) pp:1739-1749
Publication Date(Web):June 2006
DOI:10.1016/j.jssc.2006.03.002
Two novel gallium diphosphonates, (C5H5N)Ga3F(O3PC2H4PO3)2 (I) (triclinic, P-1, a=8.2880(12) Å, b=11.7197(16) Å, c=11.7601(17) Å, α=71.589(3)°, β=70.577(3)°, γ=77.313(3)°, V=1013.7(2) Å3, Z=2, R1=0.0352, wR2=0.0980) and (C5H5NH)2[Ga4F2(O3PC2H4PO3)3] (II) (triclinic, P-1, a=8.670(4) Å, b=9.742(3) Å, c=10.406(2) Å, α=81.44(3)°, β=65.83(5)°, γ=67.16(3)°, V=739.0(4) Å3, Z=2, R1=0.0600, wR2=0.1495) have been synthesised by solvothermal methods in the presence of pyridine and their structures determined using single-crystal X-ray diffraction data. Both compounds I and II are composed of various Ga-centered polyhedra and ethylenediphosphonate groups that link together to form framework materials with one- and two-dimensional channel systems, respectively. The two structures are formed in the presence of structure-directing pyridine molecules that are directly bound to some of the Ga atoms in I, and are protonated as pyridinium cations in II. Compounds I has a charge-neutral framework, while compound II has an anionic framework. Both materials provide rare examples of organically structure-directed framework metal diphosphonate materials.(C5H5N)Ga3F(O3PC2H4PO3)2 (I) and (C5H5NH)2[Ga4F2(O3PC2H4PO3)3] (II) are novel gallium diphosphonate materials composed of Ga-centered polyhedra and ethylenediphosphonate groups that link together to form framework materials with one- and two-dimensional channel systems, respectively. The two structures are formed in the presence of structure-directing pyridine molecules or pyridinium cations and are examples of organically structure-directed framework metal diphosphonates.
Co-reporter:Martin P. Attfield, Yousef Al-Ebini and Patrick Hill
Journal of Materials Chemistry A 2010 - vol. 20(Issue 39) pp:NaN8692-8692
Publication Date(Web):2010/09/07
DOI:10.1039/C0JM01429J
The core/shell composite silicogermanate zeotype material, Si-ASU-7, has been prepared in a one-step solvothermal synthesis process from a reactant mixture of GeO2 and SiO2 in a dimethylamine/H2O/HF solvent mixture. The core/shell nature of the product material has been determined using a combination of X-ray diffraction on powder and single crystal samples, and energy dispersive X-ray spectroscopy. The crystal structure of Si-ASU-7, ([Si0.221Ge0.779O2]10·(Me2NH)(H2O), tetragonal, space group P4/mnc, a = 12.3484(3) Å, c = 14.3979(5) Å, V = 2195.43(11) Å3) determined using single crystal X-ray diffraction data indicates that incorporation of silicon into the structure introduces a degree of disorder to the orientation of the double 4-ring secondary building units from which the framework is constructed. The thermal stability of the as-synthesised composite Si-ASU-7 material is enhanced compared to the pure germanate material ASU-7.
Co-reporter:Neena S. John, Camilla Scherb, Maryiam Shöâeè, Michael W. Anderson, Martin P. Attfield and Thomas Bein
Chemical Communications 2009(Issue 41) pp:NaN6296-6296
Publication Date(Web):2009/09/07
DOI:10.1039/B908299A
In situ
atomic force microscopy was used to directly investigate the growth processes of the oriented metal–organic framework HKUST-1 grown on self-assembled monolayers on gold.
Co-reporter:Martin P. Attfield and Pablo Cubillas
Dalton Transactions 2012 - vol. 41(Issue 14) pp:NaN3878-3878
Publication Date(Web):2011/12/19
DOI:10.1039/C2DT12006B
Nanoporous metal organic frameworks (MOFs) form one of the newest families of crystalline nanoporous material that is receiving worldwide attention. Successful use of MOFs for application requires not only development of new materials but also a need to control their crystal properties such as size, morphology, and defect concentration. An understanding of the crystal growth processes is necessary in order to aid development of routes to control such properties of the crystallites. In this Perspective article we aim to provide a short overview of the current work and understanding concerning the nucleation and growth processes of nanoporous MOFs and how this work may be expanded upon to further our comprehension of this subject. We also focus heavily on in situ studies that provide real time information on the developing materials and generally provide the most conclusive findings on the processes under investigation.
![Cobalt, tris[μ-[1,4-benzenedicarboxylato(2-)-κO1:κO'1]]-μ -oxotetra-](/data/chemimg/3800300/916459-12-6.png)
![Cobalt, tris[μ-[1,4-benzenedicarboxylato(2-)-κO1:κO'1]]-μ -oxotetra-](/data/chemimg/3800300/916459-12-6_b.png)