A5006292664- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organic and Molecular Conductors Research
- Magnetism in coordination complexes
- Metal-Organic Frameworks: Synthesis and Applications
- Crystallography and molecular interactions
- Perovskite Materials and Applications
- Conducting polymers and applications
- Covalent Organic Framework Applications
- Advanced NMR Techniques and Applications
- Nuclear physics research studies
- Porphyrin and Phthalocyanine Chemistry
- Electron Spin Resonance Studies
- Polyoxometalates: Synthesis and Applications
- Inorganic Fluorides and Related Compounds
- Advanced Nanomaterials in Catalysis
- Supramolecular Chemistry and Complexes
- Membrane Separation Technologies
- Boron Compounds in Chemistry
- Organometallic Complex Synthesis and Catalysis
- Peptidase Inhibition and Analysis
- Lanthanide and Transition Metal Complexes
- Quantum chaos and dynamical systems
- Chaos control and synchronization
- 2D Materials and Applications
The University of Sydney
2013-2022
University of Auckland
2005
Memorial Sloan Kettering Cancer Center
2005
Abstract A major challenge is the development of multifunctional metal–organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing redox active ligand tetra(4‐pyridyl)tetrathiafulvalene (TTF(py) 4 ) spin‐crossover Fe II centers. The materials exhibit activity, in addition to thermally photo‐induced spin crossover (SCO). crystal‐to‐crystal transformation induced I 2 doping has also been...
Donor–acceptor charge transfer interactions in a tetrathiafulvalene–naphthalene diimide-based metal–organic framework (MOF) are interrogated using complementary suite of solid state spectroscopic, electrochemical and spectroelectrochemical methods along with computational calculations.
The first porous molecular conductor (PMC), which exhibits porosity, a through-space conduction pathway and rich charge carriers (electrons), was prepared through electrocrystallization from Cd2+ N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxdiimide (NDI-py). [Cd(NDI-py)(OH2)4](NO3)1.3±0.1·nDMA (PMC-1) assembled by π–π stacking among one-dimensional (1D) linear coordination polymers. NDI cores were partially reduced into radical anions to form conductive π-stacked columns, yielding...
The fundamentally important phenomenon of mixed valency has been discussed in detail over the past 50 years, predominantly context dinuclear complexes, which are used as model systems for understanding electron delocalization more complex biological and physical systems. Very recently, shown to be an mechanism charge transfer, leading conductivity two- three-dimensional framework materials such metal–organic frameworks related including covalent organic semicrystalline semiconducting...
A new microporous framework, Zn(NDC)(DPMBI) (where NDC = 2,7-naphthalene dicarboxylate and DPMBI N,N′-di-(4-pyridylmethyl)-1,2,4,5-benzenetetracarboxydiimide), containing the redox-active benzenetetracarboxydiimide (also known as pyromellitic diimide) ligand core has been crystallographically characterised exhibits a BET surface area of 608.2 ± 0.7 m2 g−1. The crystallinity material is retained upon chemical reduction with sodium naphthalenide (NaNp), which generates monoradical anion...
Seven new coordination polymers based on the redox-active tetra(4-pyridyl)-tetrathiafulvalene ligand (TTF(py)4) and different transition-metal ions, namely, {[Cu(hfac)2][TTF(py)4]·2(CH2Cl2)}n (1), {[Co(acac)2][TTF(py)4]0.5·(CHCl3)}n (2), {[Mn(hfac)2][TTF(py)4]0.5}n (3), {[Cu2(OAc)4][TTF(py)4]0.5·1.5(CHCl3)·0.5(H2O)·(CH3CN)}n (4), {[Mn(SCN)2][TTF(py)4]·6(CH2Cl2)}n (5), {[Mn(SeCN)Cl][TTF(py)4]}n (6), {Cu2[TTF(py)4]2·(ClO4)2·2.5(CH2Cl2)·1.5(CH3CN)}n (7), were synthesized characterized. The...
A concerted bending–flattening motion of the redox-active TTF within constructed one-dimensional Fe<sup>II</sup>–TTF–Schiff-base chain with bridging 4,4′-bpy enhances dielectric constant coupled to its spin-crossover transition above room temperature.
Four new polymeric metal compounds based on the redox-active tetrathiafulvalene-tetrabenzoate ligand and different divalent cations (Co(II), Cd(II), Ba(II)), including {[Co2(TTFTB)(2,2′-Bpy)2(H2O)2]·DMF·2H2O}n (1), {[Co2(TTFTB)(4,4′-Bpy)(H2O)6]·DMF}n (2), {[Cd(H2TTFTB)(Bpea)(H2O)2]·DMF·3H2O}n (3), {[Ba(H2TTFTB)(H2O)2]·DMF·C2H5OH}n (4) (2,2′-Bpy = 2,2′-bipyridine, 4,4′-Bpy 4,4′-bipyridine, Bpea 1,2-bis(4-pyridyl)ethane), were synthesized characterized. The versatile tetracarboxylate was...
In search of multifunctional metal–organic frameworks (MOFs), redox-active donors and acceptors, namely, tetrathiafulvalene (TTF) 7,7,8,8-tetracyanoquinodimethane (TCNQ), were concomitantly used as skeletal components with diamagnetic metal nodes (Cd Zn) to construct unique framework materials. Six isostructural synthesized by diffusion salts, TTF(py)4, either paramagnetic Li(TCNQ) or H2TCNQ. They characterized single-crystal X-ray diffraction FT-IR UV–vis–NIR spectroscopy, their physical...
The new one-dimensional coordination framework (Zn(DMF)NO3)2(NDC)(DPMNI), where NDC = 2,6-naphthalenedicarboxylate and DPMNI N,N'-bis(4-pyridylmethyl)-1,4,5,8-naphthalenetetracarboxydiimide, which has been crystallographically characterized, exhibits two redox-accessible states due to the successive reduction of naphthalenediimide (NDI) ligand core. Solid-state electrochemical vis-near-IR spectroelectrochemical measurements coupled with density functional theory (DFT) calculations enabled...
The stimuli responsive behaviour of charge transfer donor-acceptor metal-organic frameworks (MOFs) remains an understudied phenomenon which may have applications in tuneable electronic materials. We now report the modification characteristics a semiconducting tetrathiafulvalene-naphthalene diimide-based MOF under applied electrochemical bias and pressure. employ facile solid state situ Raman spectroelectrochemical technique, for first time characterisation electroactive MOFs, to monitor...
Abstract A major challenge is the development of multifunctional metal–organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing redox active ligand tetra(4‐pyridyl)tetrathiafulvalene (TTF(py) 4 ) spin‐crossover Fe II centers. The materials exhibit activity, in addition to thermally photo‐induced spin crossover (SCO). crystal‐to‐crystal transformation induced I 2 doping has also been...
Abstract Using the redox‐active tetrathiafulvalene tetrabenzoate (TTFTB 4− ) as linker, a series of stable and porous rare‐earth metal–organic frameworks (RE‐MOFs), [RE 9 (μ 3 ‐OH) 13 ‐O)(H 2 O) (TTFTB) ] ( 1‐RE , where RE=Y, Sm, Gd, Tb, Dy, Ho, Er) were constructed. The RE ‐O) (H ](CO 12 clusters within act segregated single‐molecule magnets (SMMs) displaying slow relaxation. Interestingly, upon oxidation by I S= 0 TTFTB linkers converted into S = .3− radical which introduced...
A combined spectroscopic and structural study was undertaken to investigate the nature of incorporation electron acceptor guest 7,7,8,8-tetracyanoquinodimethane (TCNQ) closely related tetracyanoethylene (TCNE) into host porous framework [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate)—a guest–host system recently shown be highly conductive. We find that concentration in can modulated via synthesis reaction time temperature. suite spectroscopic, X-ray neutron powder diffraction, density...
Redox reactions on electroactive donor–acceptor polymers can be used to tune their response external magnetic and electrical stimuli.
Experiments show that the addition of small amounts polymer to a Newtonian fluid undergoing chaotic advection decreases amount chaos; regular or unmixed regions increase in size and squeeze out behavior while preserving underlying symmetries. The islands increases with increasing elasticity rate stirring. Large effects are present at relatively low Deborah numbers (relaxation time scale flow).
Three new Mn(II) coordination polymers (CPs) derived from the redox-active tetra(4-pyridyl)-tetrathiafulvalene ligand (TTF(py)4), namely, {[MnCl2(TTF(py)4)]·4CH2Cl2·CH3OH}n (1), {[Mn(N3)(TTF(py)4)]·(ClO4)·2CHCl3·CH3OH)}n (2), and {[Mn(dca)2(TTF(py)4)0.5]·CH3OH}n (3) (dca = dicyanamide), were synthesized characterized. Their topology dimensionality are dependent on counteranion used: Cl– forms a two-dimensional network, N3– induces (4,6)-connected binodal sqc11-type three-dimensional (3D)...
Abstract The new π-extended redox-active ligand with both TTF and triazole units, 6-(4,5-bis(propylthio)-1,3-dithiol-2-ylidene)-1H-[1,3]dithiolo[4′,5′:4,5]benzo [1,2-d] [1–3]triazole, has been successfully prepared. Based on the versatile Cu(tta) 2 precursors (tta − = 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione), a TTF-based pentanuclear Cu II cluster (Cu 5 (tta) 4 (TTFN 3 ) 6 is synthesized structurally characterized. Their absorption electrochemical properties are investigated....
A one-dimensional FeII coordination polymer (CP) has been formed which includes the redox-active ligand bis-pyridyltetrathiafulvalene (py2TTF) and a Schiff base-like N2O2 ligand. This CP is both spin crossover (SCO) in solid-state, chemical oxidation results SCO modification.