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Journal articleWilson LE, Hassenrueck C, Winter RF, et al., 2016,
Functionalised Biferrocene Systems towards Molecular Electronics
, European Journal of Inorganic Chemistry, Vol: 2017, Pages: 496-504, ISSN: 1434-1948Biferrocene systems offer a motif that incorporates multiple redox-active centres, enabling redox control, high levels of stability and near perfect conductance levels, and thus is an ideal participant within future molecular electronic systems. However, the incorporation of biferrocene can be restricted by current synthetic routes. Herein, we discuss a new method for the synthesis and incorporation of biferrocenyl motifs within extended conjugated systems. We have synthesised a family of compounds featuring biferrocenyl–ethynyl units with various pendant heteroaromatic linkages. The new compounds are probed with use of cyclic voltammetry, UV/Vis/near-infrared (NIR) spectroelectrochemistry and X-ray crystallography to gain further understanding of their structural and electronic properties.
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Journal articleLemmer M, Inkpen MS, Kornysheva K, et al., 2016,
Unsupervised vector-based classification of single-molecule charge transport data
, Nature Communications, Vol: 7, Pages: 1-10, ISSN: 2041-1723The stochastic nature of single-molecule charge transport measurements requires collection of large data sets to capture the full complexity of a molecular system. Data analysis is then guided by certain expectations, for example, a plateau feature in the tunnelling current distance trace, and the molecular conductance extracted from suitable histogram analysis. However, differences in molecular conformation or electrode contact geometry, the number of molecules in the junction or dynamic effects may lead to very different molecular signatures. Since their manifestation is a priori unknown, an unsupervised classification algorithm, making no prior assumptions regarding the data is clearly desirable. Here we present such an approach based on multivariate pattern analysis and apply it to simulated and experimental single-molecule charge transport data. We demonstrate how different event shapes are clearly separated using this algorithm and how statistics about different event classes can be extracted, when conventional methods of analysis fail.
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Journal articlePan J, Harriss BI, Chan CF, et al., 2016,
Gallium and Functionalized-Porphyrins Combine to Form Potential Lysosome-Specific Multimodal Bioprobes
, Inorganic Chemistry, Vol: 55, Pages: 6839-6841, ISSN: 1520-510XA water-soluble bimetallic normal ("cold") and radiochemical ("hot") gallium-porphyrin-ruthenium-bipyridine complex (GaporRu-1) has been synthesized by microwave methodology in short reaction times with good (>85%) yields. (68)GaporRu-1 is demonstrated to be a potential multimodal and functional bioprobe for positron emission tomography (PET), lysosome specific optical imaging, and photodynamic therapy.
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Journal articleInkpen MS, Scheerer S, Linseis M, et al., 2016,
Oligomeric ferrocene rings
, Nature Chemistry, Vol: 8, Pages: 825-830, ISSN: 1755-4330Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1′-disubstituted ferrocene units (cyclo[n], n = 5–7, 9). Due to the close proximity and connectivity of centres (covalent Cp–Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e– waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼107 s−1), these molecules can be considered as uniformly charged nanorings (diameter ∼1–2 nm).
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Conference paperMcCluskey S, Plisson C, Wells L, et al., 2016,
Evaluation of phosphonium cations as imaging agents for cardiac energetics and dysfunction
, Publisher: SOC NUCLEAR MEDICINE INC, ISSN: 0161-5505 -
Conference paperFarnaby J, Hickson J, Long N, 2016,
Synthetic routes to multi-metallic f-element complexes with redox-active ligands
, Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727 -
Book chapterPhanopoulos A, Long NJ, Miller PW, 2016,
Triphosphine ligands: coordination chemistry and recent catalytic applications
, The Chemical Bond III, Editors: Mingos, Publisher: Springer, Pages: 31-61Phosphines are a long established class of ligand that are known to form a vast array of transition metal complexes. They behave as neutral electron pair donors, or Lewis bases, that alter the solubility and stereoelectronic properties of the metal centre. A key motivation for their continued development is for homogeneous catalysis. For over five decades, transition metal–phosphine complexes have been used for catalytic reactions, mainly exploiting monodentate or bidentate phosphine ligands. Multidentate phosphines by comparison have received much less attention in part because they tend to form more stable complexes with a saturated coordination environment around the metal centre. Recent developments in the areas of catalytic reduction of carboxylic acid derivatives using molecular hydrogen and in the field of biomass up-conversion have exploited catalysts based on tridentate phosphines. This chapter highlights the use of these multidentate phosphines for synthesis of coordination complexes and discusses some of their recent applications in homogeneous catalysis.
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Journal articlePhanopoulos A, White AJP, Long NJ, et al., 2016,
Insight into the stereoelectronic parameters of N-triphos ligands via coordination to tungsten(0)
, Dalton Transactions, Vol: 45, Pages: 5536-5548, ISSN: 1477-9226A series of new N-triphos tungsten complexes have been synthesised and structurally characterised. The coordination behaviour of a range of N-triphos (N(CH2PR2)3, NP3R) ligands, and a mixed-arm diphosphine-pyridyl (PPNCyh) ligand were explored. The steric and electronic parameters of five N-triphos ligands: NP3Ph, NP3iPr, NP3Cyp, NP3Cyh and NP3PhF2, and the carbon-centred triphos ligand, CH3C(CH2PPh2)3 (MeCP3Ph), were established. Steric parameters were evaluated by analysing the cone angles calculated from X-ray crystal structures, whilst the electron-donating ability of the ligands was determined from 31P–77Se NMR coupling constants of selenium derivatives and the IR carbonyl stretching frequencies across a series of tungsten–carbonyl complexes. In general, electron-rich phosphines formed bidentate complexes while less electron-rich ligands coordinated in a tridentate mode, regardless of steric bulk. An indirect interaction between the apical nitrogen of the ligand and metal centre is implicated for tridentate complexes and is supported through DFT calculations and analysis of N-protonated complexes. Complexes 1, 3, 4, 6–8 and 10 were characterised by single-crystal X-ray crystallography.
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Journal articleKumar S, Johnson TW, Wood CK, et al., 2016,
Template-Stripped Multifunctional Wedge and Pyramid Arrays for Magnetic Nanofocusing and Optical Sensing
, Acs Applied Materials & Interfaces, Vol: 8, Pages: 9319-9326, ISSN: 1944-8252We present large-scale reproducible fabrication of multifunctional ultrasharp metallic structures on planar substrates with capabilities including magnetic field nanofocusing and plasmonic sensing. Objects with sharp tips such as wedges and pyramids made with noble metals have been extensively used for enhancing local electric fields via the lightning-rod effect or plasmonic nanofocusing. However, analogous nanofocusing of magnetic fields using sharp tips made with magnetic materials has not been widely realized. Reproducible fabrication of sharp tips with magnetic as well as noble metal layers on planar substrates can enable straightforward application of their material and shape-derived functionalities. We use a template-stripping method to produce plasmonic-shell-coated nickel wedge and pyramid arrays at the wafer-scale with tip radius of curvature close to 10 nm. Further we explore the magnetic nanofocusing capabilities of these ultra-sharp substrates deriving analytical formulas and comparing the results with computer simulations. These structures exhibit nanoscale spatial control over the trapping of magnetic microbeads and nanoparticles in solution. Additionally, enhanced optical sensing of analytes by these plasmonic-shell-coated substrates is demonstrated using surface-enhanced Raman spectroscopy. These methods can guide the design and fabrication of novel devices with applications including nanoparticle manipulation, biosensing, and magnetoplasmonics.
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Journal articleInkpen MS, White AJP, Albrecht T, et al., 2016,
Complexes comprising ‘dangling’ phosphorus arms and tri(hetero)metallic butenynyl moieties
, Journal of Organometallic Chemistry, Vol: 812, Pages: 145-150, ISSN: 1872-8561Trans-RuCl2(PP3)2 (1a) (PP3 = tris[2-(diphenylphosphino)ethyl]phosphine) was prepared by reaction of RuCl2(PPh3)3 with 2 eq. PP3. Through coordination of two potentially tetradentate ligands in a bidentate arrangement, four uncoordinated phosphine moieties remain readily available for subsequent reaction. This is demonstrated through their facile oxidation with hydrogen peroxide, providing trans-RuCl2(PP[Pdouble bond; length as m-dashO]2)2 (1b) (PP[Pdouble bond; length as m-dashO]2 = bis[2-(diphenylphosphine oxide)ethyl][2-(diphenylphosphino)ethyl]phosphine). Whilst chloride abstraction reactions from 1a appear slow (typical for trans dichlorides), cis-RuCl2(PP3) is shown to react rapidly with ethynylferrocene under ‘Dixneuf’ conditions (CH2Cl2, NaPF6, NEt3), providing the tri(hetero)metallic butenynyl complex [(PP3)Ru(η3–FcC3CHFc)]PF6 (2, Fc = ferrocenyl). The pendant groups of 1a-b offer great potential for future coordination studies (for example, to prepare mixed transition metal/lanthanide materials), whereby the facile synthetic route to 2 suggests a path towards examination of complex mixed-valence systems comprising multiple redox-active centres.
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Journal articleLaurent D, Vinet L, Lamprianou S, et al., 2016,
Pancreatic β-cell imaging in humans: fiction or option?
, Diabetes Obesity & Metabolism, Vol: 18, Pages: 6-15, ISSN: 1462-8902Diabetes mellitus is a growing worldwide epidemic disease, currently affecting 1 in 12 adults. Treatment of disease complications typically consumes ∼10% of healthcare budgets in developed societies. Whilst immune-mediated destruction of insulin-secreting pancreatic β cells is responsible for Type 1 diabetes, both the loss and dysfunction of these cells underly the more prevalent Type 2 diabetes. The establishment of robust drug development programmes aimed at β-cell restoration is still hampered by the absence of means to measure β-cell mass prospectively in vivo, an approach which would provide new opportunities for understanding disease mechanisms and ultimately assigning personalized treatments. In the present review, we describe the progress towards this goal achieved by the Innovative Medicines Initiative in Diabetes, a collaborative public–private consortium supported by the European Commission and by dedicated resources of pharmaceutical companies. We compare several of the available imaging methods and molecular targets and provide suggestions as to the likeliest to lead to tractable approaches. Furthermore, we discuss the simultaneous development of animal models that can be used to measure subtle changes in β-cell mass, a prerequisite for validating the clinical potential of the different imaging tracers.
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Journal articleInkpen MS, Du S, Hildebrand M, et al., 2015,
The unusual redox properties of fluoroferrocenes revealed through a comprehensive study of the haloferrocenes
, Organometallics, Vol: 34, Pages: 5461-5469, ISSN: 1520-6041We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1′-dihaloferrocene (fcX2) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1′-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1′-difluoroferrocene (fcF2) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1′-dichloroferrocene (fcCl2), were utilized as model systems to probe the limits of a previously reported “oxidative purification” methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX2 series. This counterintuitive result is discussed with reference to the spectroscopic, structural, and first-principles calculations of these and related materials.
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Journal articleLong NJ, Stasiuk G, Gallo J, et al., 2015,
Tuning the relaxation rates of dual mode T1/T2 nanoparticle contrast agents: a study into the ideal system
, Nanoscale, Vol: 7, Pages: 16119-16128, ISSN: 2040-3372Magnetic resonance imaging (MRI) is an excellent imaging modality. However the low sensitivity of the technique poses a challenge to achieving an accurate image of function at the molecular level. To overcome this, contrast agents are used; typically gadolinium based agents for T1 weighted imaging, or iron oxide based agents for T2 imaging. Traditionally, only one imaging mode is used per diagnosis although several physiological situations are known to interfere with the signal induced by the contrast agents in each individual imaging mode acquisition. Recently, the combination of both T1 and T2 imaging capabilities into a single platform has emerged as a tool to reduce uncertainties in MR image analysis. To date, contradicting reports on the effect on the contrast of the coupling of a T1 and T2 agent have hampered the application of these specialised probes. Herein, we present a systematic experimental study on a range of gadolinium-labelled magnetite nanoparticles envisioned to bring some light into the mechanism of interaction between T1 and T2 components, and advance towards the design of efficient (dual) T1 and T2 MRI probes. Unexpected behaviours observed in some of the constructs will be discussed. In this study, we demonstrate that the relaxivity of such multimodal probes can be rationally tuned to obtain unmatched potentials in MR imaging, exemplified by preparation of the magnetite-based nanoparticle with the highest T2 relaxivity described to date.
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Conference paperDuerrbeck A, Hor A, Long N, 2015,
New highly-emissive soluble dynamic Eu(III) coordination polymers for Ln(III) and transition metal sensing applications
, Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727 -
Conference paperMiller P, Phanopoulos A, Long N, 2015,
Direct conversion of levulinic acid to 2-methyltetrahydrofuran using discrete Ru and Rh N-triphos catalysts
, Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727
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