ORCID Profile
0000-0003-1084-1287
Current Organisations
University of Adelaide
,
Flinders University
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In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Electrical and Electronic Engineering | Mineral Processing/Beneficiation | Macromolecular and Materials Chemistry | Synthesis of Materials | Decision Support and Group Support Systems | Nanochemistry and Supramolecular Chemistry | Control Systems, Robotics and Automation
Expanding Knowledge in the Chemical Sciences | Beneficiation or Dressing of Iron Ores | Mining and Extraction of Precious (Noble) Metal Ores | Mining and Extraction of Copper Ores |
Publisher: Elsevier BV
Date: 12-2011
Publisher: Springer Science and Business Media LLC
Date: 14-07-2022
DOI: 10.1038/S41598-022-15663-Z
Abstract: Metal–organic frameworks (MOFs) with ratiometric sensing properties are desirable for many applications due to their intrinsic self-calibration. We report the re-assessment of the sensing properties of a MOF, originally reported as containing europium(III) and 2-hydroxyterephtalic acid, and having fluorescent ratiometric iron(III) sensing properties. Synchrotron single-crystal X-ray diffraction and proton nuclear magnetic resonance ( 1 H NMR) spectroscopy revealed that the MOF is composed of 2-methoxyterephthalate, not 2-hydroxyterephthalate as originally reported. We found that the MOF exhibits a sensor turn-off response towards Fe 3+ ion concentrations in the range 0.5–3.7 ppm (band 425 nm), and a turn-on response towards a decrease of pH from 5.4 to 3.0 (band 375 nm), both resulting from the addition of acidic Fe 3+ salt solution to a MOF suspension. Thus, the ratiometric sensing properties and the originally proposed mechanism no longer apply our work reveals a dynamic quenching mechanism for the fluorescence turn-off response due to the presence of Fe 3+ ions, and a ligand protonation mechanism for the turn-on response to a decrease in pH. Our work highlights the importance of a thorough investigation of the structure of any newly synthesized MOF, and, in the case of potential sensors, their selectivity and any environmental effects on their sensing behavior.
Publisher: American Chemical Society (ACS)
Date: 04-09-2012
DOI: 10.1021/OL301715U
Abstract: A total synthesis of the marine sponge meroterpenoid (+)-aureol has been achieved in 12 steps (6% overall yield) from (+)-sclareolide. Key steps of the synthesis include a biosynthetically inspired sequence of 1,2-hydride and methyl shifts, and a biomimetic cycloetherification reaction.
Publisher: American Chemical Society (ACS)
Date: 03-08-2022
DOI: 10.1021/ACS.INORGCHEM.2C02046
Abstract: Porous structures based on multi-metallic motifs are receiving growing interest, but their general preparation still remains a challenge. Here, we report the self-assembly and structure of a Cu
Publisher: The Royal Society
Date: 13-01-2017
Abstract: Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4CC09639H
Abstract: Post-synthetic metallation is a key route to modifying MOFs but as shown here the choice of solvent affects the extent of reaction and the form of the metallated product.
Publisher: Georg Thieme Verlag KG
Date: 17-12-2012
Publisher: Wiley
Date: 14-01-2022
Abstract: A fluxional bis‐monodentate ligand, based on the archetypal shape‐shifting molecule bullvalene, self‐assembles with M 2+ (M=Pd 2+ or Pt 2+ ) to produce a highly complex ensemble of permanently fluxional coordination cages. Metal‐mediated self‐assembly selects for an M 2 L 4 architecture while maintaining shape‐shifting ligand complexity. A second level of simplification is achieved with guest‐exchange the binding of halides within the M 2 L 4 cage mixture results in a convergence to a cage species with all four ligands present as the “B isomer”. Within this confine, the reaction graph of the bullvalene is greatly restricted, but gives rise to a mixture of 38 possible diastereoisomers in rapid exchange. X‐ray crystallography reveals a preference for an achiral form consisting of both ligand enantiomers. Through a combination of NMR spectroscopy and DFT calculations, we elucidate the restricted isomerisation pathway of the permanently fluxional M 2 L 4 assembly.
Publisher: Wiley
Date: 30-07-2018
Publisher: Wiley
Date: 23-05-2017
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CE41244J
Publisher: American Chemical Society (ACS)
Date: 17-05-2023
DOI: 10.1021/JACS.3C03239
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CC17440E
Abstract: A silver(I) 3-D porous coordination polymer (PCP, 1) with a sodalite topology undergoes a remarkable reversible crystal-to-crystal expansion and contraction upon exposure to different solvents. Notably, complete desolvation of 1 also facilitates a transformation to a non-porous 2-D coordination polymer (2).
Publisher: Wiley
Date: 22-03-2018
Abstract: The self‐assembly of eight Pd II cations and sixteen phenanthrene‐derived bridging ligands with 60° bite angles yielded a novel M 8 L 16 metallosupramolecular architecture composed of two interlocked D 4 h ‐symmetric barrel‐shaped containers. Mass spectrometry, NMR spectroscopy, and X‐ray analysis revealed this self‐assembled structure to be a very large “Hopf link” catenane featuring channel‐like cavities, which are occupied by NO 3 − anions. The importance of the anions as catenation templates became imminent when we observed the nitrate‐triggered structural rearrangement of a mixture of M 3 L 6 and M 4 L 8 assemblies formed in the presence of BF 4 − anions into the same interlocked molecule. Furthermore, the densely packed structure of the M 8 L 16 catenane was exploited in the preparation of a hexyloxy‐functionalized analogue, which further self‐assembled into vesicle‐like aggregates in a reversible manner.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC03379F
Abstract: In this review, we highlight recent approaches that facilitate integrative self-sorting of ’naked’ metal ions and ligands to form multi-component, heteroleptic cage structures.
Publisher: American Chemical Society (ACS)
Date: 21-08-2019
Publisher: Frontiers Media SA
Date: 25-05-2021
DOI: 10.3389/FCHEM.2021.696081
Abstract: The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu 2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu 4 L 4 lantern cage ( 1 ). Importantly, we show control over the coordinative propensity of the exterior amine of the ligand, which enables us to isolate a crystalline, two-dimensional metal-organic framework composed entirely of MOC units ( 2 ). Furthermore, we show that the nucleophilicity of the exterior amine of 1 can be accessed in solution to generate a cross-linked cage polymer ( 3 ) via imine condensation.
Publisher: Informa UK Limited
Date: 26-11-2015
Publisher: Wiley
Date: 02-07-2015
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16663
Abstract: The chemical mutability of metal–organic frameworks (MOFs) is an advantageous feature that allows fine-tuning of their physical and chemical properties. Herein, we report the successful isoreticulation of a MOF with an outstanding gas selectivity for CO2 versus N2: [Cu(L1)(H2O)]·xS (CuL1), where H2L1 = bis(4-(4-carboxyphenyl)-1H-pyrazolyl)methane) and S = solvate. By modifying the steric bulk and length of the original ligand, we synthesised three new MOFs with 2D networks isoreticular to CuL1, namely [Cu(L1Me)(H2O)]·xS (CuL1Me), [Cu(L2)(H2O)]·xS (CuL2), and [Cu(L2Me)(H2O)]·xS (CuL2Me) (where H2L1Me = bis(4-(4-carboxyphenyl)-3,5-dimethyl-1H-pyrazolyl)methane, H2L2 = bis(4-(4-carboxyphenyl)-(ethyne-2,1-yl)-1H-pyrazolyl)methane, and H2L2Me = bis(4-(4-carboxyphenyl)-(ethyne-2,1-yl)-3,5-dimethyl-1H-pyrazolyl)methane). Depending on the steric hindrance and structure metrics of the organic links, staggered and eclipsed arrangements of 2D 44 net layers were obtained. The anisotropy of the pore dimensions is proportional to the linker length (L2 and L2Me), which when increased, renders these materials non-porous. However, the more sterically demanding ligand L1Me gives a material that shows gate-opening behaviour in response to a CO2 absorbate. The synthesis and structure of an unexpected mixed-valence CuII/CuI 3D MOF, Cu3[Cu(L2Me)2]2(H2O)4]·xS (Cu5(L2Me)4), containing an unusual trimeric CuII node are also reported.
Publisher: CSIRO Publishing
Date: 2019
DOI: 10.1071/CH19215
Abstract: Understanding the key features that determine structural flexibility in metal–organic frameworks (MOFs) is key to exploiting their dynamic physical and chemical properties. We have previously reported a 2D MOF material, CuL1, comprising five-coordinate metal nodes that displays exceptional CO2/N2 selectively (L1=bis(4-(4-carboxyphenyl)-1H-pyrazolyl)methane). Here we examine the effect of utilising six-coordinate metal centres (CoII and NiII) in the synthesis of isostructural MOFs from L1, namely CoL1 and NiL1. The octahedral geometry of the metal centre within the MOF analogues precludes an ideal eclipse of the 2D layers, resulting in an offset stacking, and in certain cases, the formation of 2-fold interpenetrated analogues β-CoL1 and β-NiL1. We used a combination of thermogravimetric analysis (TGA), and powder and single crystal X-ray diffraction (PXRD and SCXRD) to show that desolvation is accompanied by a structural change for NiL1, and complete removal of the coordinated H2O ligands results in a reduction in long-range order. The offset nature of the 2D layers in combination with the structural changes impedes the adsorption of meaningful quantities of gases (N2, CO2), highlighting the importance of a five-coordinate metal centre in achieving optimal pore accessibility for this family of flexible materials.
Publisher: American Chemical Society (ACS)
Date: 26-09-2012
DOI: 10.1021/OL302524Q
Abstract: The polycyclic polyprenylated acylphloroglucinol natural product garcibracteatone has been synthesized in four steps from phloroglucinol, using a strategy based on biosynthetic speculation. The key biomimetic transformation is a cascade of 7-endo-trig and 5-exo-trig radical cyclizations followed by a terminating aromatic substitution reaction.
Publisher: Wiley
Date: 16-09-2015
Abstract: Open‐framework materials, such as metal–organic frameworks (MOFs) and coordination polymers have been widely investigated for their gas adsorption and separation properties. However, recent studies have demonstrated that their highly crystalline structures can be used to periodically organize guest molecules and non‐structural metal compounds either within their pore voids or by anchoring to their framework architecture. Accordingly, the open framework can act as a matrix for isolating and elucidating the structures of these moieties by X‐ray diffraction. This concept has broad scope for development as an analytical tool where obtaining single crystals of a target molecule presents a significant challenge and it additionally offers potential for obtaining insights into chemically reactive species that can be stabilized within the pore network. However, the technique does have limitations and as yet a general experimental method has not been realized. Herein we focus on recent ex les in which framework materials have been utilized as a scaffold for ordering molecules for analysis by diffraction methods and canvass areas for future exploration.
Publisher: American Chemical Society (ACS)
Date: 06-10-2016
DOI: 10.1021/JACS.6B08694
Abstract: Due to the inherent difficulties in achieving a defined and exclusive formation of multicomponent assemblies against entropic predisposition, we present the rational assembly of a heteroleptic [Pd
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2CC04969D
Abstract: The solution-state structure of an amine-functionalised Cu
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CC00700J
Abstract: Simulation and experimental data show that network topology and chemical functionality are crucial parameters for CO 2 adsorption in an interpenetrated MOF.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CE00082G
Abstract: Controlling the particle size of a flexible metal–organic framework demonstrates that a 2D to 3D transformation gives a kinetically-trapped, structurally-locked form.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1SC05663H
Abstract: A new strategy to design atomically precise multivariate metal–organic frameworks is presented. This is achieved by linking two preformed metal–organic cages via a precisely tuned Rh–aniline interaction.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0CC08076D
Abstract: Structural asymmetry is introduced into porous Cu 4 L 4 metal–organic cages through the crystallisation-driven convergence of a dynamic combinatorial library.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CC05349J
Abstract: A covalent deprotection strategy facilitates the self-polymerisation of amine-functionalised Cu 4 L 4 metal–organic cages into supramolecular coordination polymers with tunable porosity.
Publisher: Wiley
Date: 22-03-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2SC06629G
Abstract: The extreme axial twist of a Pd 2 L 4 cage facilitates tight encapsulation of mono-anions through prolate-oblate cavity adaptation. In the absence of a suitable guest, the helical cage exists in equilibrium with an ‘unwound’ mesocate isomer.
Publisher: Springer Science and Business Media LLC
Date: 07-09-2014
DOI: 10.1038/NCHEM.2045
Abstract: Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2][Rh(CO)2Cl2].
Publisher: American Chemical Society (ACS)
Date: 12-11-2021
DOI: 10.26434/CHEMRXIV-2021-TLVXW
Abstract: Using metal-organic cages (MOCs) as preformed supermolecular building-blocks (SBBs) is a powerful strategy to design functional metal-organic frameworks (MOFs) with control over the pore architecture and connectivity. However, introducing chemical complexity into the network via this route is limited as most methodologies focus on only one type of MOC as the building-block. Herein we present the pairwise linking of MOCs as a design approach to introduce defined chemical complexity into porous materials. Our methodology exploits preferential Rh-aniline coordination and stoichiometric control to rationally link Cu4L4 and Rh4L4 MOCs into chemically complex, yet extremely well-defined crystalline solids. This strategy is expected to open up significant new possibilities to design bespoke multi-functional materials with atomistic control over the location and ordering of chemical functionalities.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0SC00070A
Abstract: The crystal packing and porosity of Cu 4 L 4 metal–organic polyhedra can be controlled by exploiting their rich solvatomorphism, structural non-rigidity and amenability to covalent post-assembly modifications.
Start Date: 03-2019
End Date: 04-2023
Amount: $405,000.00
Funder: Australian Research Council
View Funded ActivityStart Date: 08-2020
End Date: 08-2026
Amount: $3,703,664.00
Funder: Australian Research Council
View Funded Activity