Exploring the cellular uptake and localisation of phosphorescent rhenium fac-tricarbonyl metallosurfactants as a function of lipophilicity.

A systematic study of the cellular uptake of emissive complexes as a function of their lipophilicity is presented. Here a series of amphiphilic rhenium fac-tricarbonyl bisimine complexes bearing axial substituted imidazole or thiazole ligands, [Re(bpy)(CO)3(ImCnHm)]+ {n = 1 m = 3 (1+), n = 4 m = 9 (2+), n = 8 m = 17 (3+), n = 12 m = 25 (4+), n = 16 m = 33 (5+), n = 2 m = 3 (6+); bpy = 2,2'-bipyridine, Im = imidazole} and [Re(bpy)(CO)3(L)]+ {L = 1-mesitylimidazole, ImMes (7+), 4,5-dimethylthiazole, dmt (8+) and 4-methyl-5-thiazole-ethanol, mte (9+)} is reported. The X-ray crystal structures of 2+, 8+ and 9+ confirm the geometry and expected distribution of ligands and indicated that the plane of the imidazole/thiazole ring is approximately parallel to the long axis of the bipy ligand.

Ligand-Tuneable, Red-Emitting Iridium(III) Complexes for Efficient Triplet-Triplet Annihilation Upconversion Performance.

A series of substituted 2-phenylquinoxaline ligands have been explored to finely tune the visible emission properties of a corresponding set of cationic, cyclometallated iridium(III) complexes. The electronic and redox properties of the complexes were investigated through experimental (including time-resolved luminescence and transient absorption spectroscopy) and theoretical methods. The complexes display absorption and phosphorescent emissions in the visible region that are attributed to metal to ligand charge-transfer transitions.

Cyclometalated cinchophen ligands on iridium(III): towards water-soluble complexes with visible luminescence.

Eight cationic heteroleptic iridium(III) complexes, [Ir(epqc)2(N^N)](+), were prepared in high yield from a cyclometalated iridium bridged-chloride dimer bearing two ethyl-2-phenylquinoline-4-carboxylate (epqc) ligands. Two X-ray crystallographic studies were undertaken on selected complexes (where the ancillary ligand N^N = 4,4'-dimethyl-2,2'-bipyridine and 4,7-diphenyl-1,10-phenanthroline) each confirming the proposed formulations, showing an octahedral coordination at Ir(III). In general, the complexes are luminescent (620-630 nm) with moderately long lifetimes indicative of phosphorescence.

Using substituted cyclometalated quinoxaline ligands to finely tune the luminescence properties of iridium(III) complexes.

The syntheses of five new heteroleptic iridium complexes [Ir(L(1-4))(2)(Diobpy)]PF(6) (where Diobpy = 4,4'-dioctylamido-2,2'-bipyridine) and [Ir(L(3))(2)(bpy)]PF(6) (where L = para-substituted 2,3-diphenylquinoxaline cyclometalating ligands; bpy = 2,2'-bipyridine) are described. The structures of [Ir(L(3))(2)(Diobpy)]PF(6) and [Ir(L(3))(2)(bpy)]PF(6) show that the complexes each adopt a distorted octahedral geometry with the expected trans-N, cis-C arrangement of the cyclometalated ligands. Electrochemical studies confirmed subtle perturbation of the Ir(III/IV) redox couple as a function of ligand variation.

Luminescent rhenium fac-tricarbonyl-containing complexes of androgenic oxo-steroids.

A new route to luminescent derivatives of androgenic steroids containing a ketone group in the 3- or 17-position has been developed. Reaction with the fac-Re(CO)(3)Cl complex of 3,3'-diamino-2,2'-bipyridine (complex 1) afforded a cyclic aminal product with different steroids. The rate of reaction and yield varies according to the conjugation or steric hindrance around the ketone group.

Enhanced photooxidation sensitizers: the first examples of cyclometalated pyrene complexes of iridium(III).

The iridium(III) cyclometalation of alkylated pyrene-benzimidazole ligands proceeds in an unprecedented manner. The resultant complexes display remarkably enhanced photooxidation capabilities using 1,5-dihydroxynaphthalene as a substrate.

Water-soluble, luminescent iridium(III)-ytterbium(III) complexes using dipyrido[3,2-a:2',3'-c]phenazine derivatives as bridging units.

Amino-substituted dipyrido[3,2-a:2',3'-c]phenazine (L(1)) and dimethyl-dipyrido[3,2-a:2',3'-c]phenazine (L(2)) have been investigated as: (i) chromophores in cyclen-based ligands for lanthanide(III) ions; (II) ancillary co-ligands in cyclometalated iridium(III) complexes; (III) bridging, linker units in covalently linked, water-soluble bimetallic lanthanide(III) iridium(III) hybrid complexes. The dipyrido[3,2-a:2',3'-c]phenazine (dppz) derivatives can act as sensitising chromophores (λ(ex) 400 nm) for Yb(III), resulting in characteristic near-IR emission at 950-1050 nm. The incorporation of dppz-type ligands into cyclometalated Ir(III) complexes of the general type [Ir(epqc)(2)(L(n))](PF(6)) (where epqc = ethylphenylquinoline carboxylate) gave luminescent species with solvent-sensitive emission properties.

Evaluation of a fluorescent derivative of AMD3100 and its interaction with the CXCR4 chemokine receptor.

AMD3100 is a potent and selective antagonist of the CXCR4 receptor; it has been shown to block the route of entry of HIV into host T-cells. This compound and its analogues have since been found to act as haematopoietic stem cell mobilisation agents and, more recently, as anti-cancer agents. Here, we have examined a fluorescent derivative of AMD3100, L(1), which offered the potential to assess the behaviour of AMD3100 at the cell surface by using optical imaging modalities.

New 2,3-disubstituted-5-hydroxyquinoxaline ligands and their coordination chemistry with cyclometallated iridium(III): syntheses, structures and tunable electronic properties.

A new series of para-substituted 2,3-diphenyl-5-hydroxyquinoxaline ligands (LH(n)) were synthesised and characterised. These ligands were prepared in high yield via a two-step synthetic method. Four novel heteroleptic iridium(III) complexes were correspondingly prepared in high yield giving [Ir(ppy)(2)(L(n))].

The co-ordination chemistry of tris(3,5-dimethylpyrazolyl)methane manganese carbonyl complexes: synthetic, electrochemical and DFT studies.

The tricarbonyl [Mn(CO)(3){HC(pz')(3)}][PF(6)] 1(+)[PF(6)](-) (pz' = 3,5-dimethylpyrazolyl) reacts with a range of P-, N- and C-donor ligands, L, in the presence of trimethylamine oxide to give [Mn(CO)(2)L{HC(pz')(3)}](+) {L = PEt(3)3(+), P(OEt)(3)4(+), P(OCH(2))(3)CEt 5(+), py 6(+), MeCN 7(+), CNBu(t)8(+) and CNXyl 9(+)}. The complex [Mn(CO)(2)(PMe(3)){HC(pz')(3)}](+)2(+) is formed by reaction of 7(+) with PMe(3). Complexes 2(+) and 6(+) were structurally characterised by X-ray diffraction methods.

Rhodium and iridium complexes of an asymmetric bicyclic NHC bearing secondary pyridyl donors.

A tridentate N^C^N ligand, 1, containing a bicyclic central NHC ring and two flanking pyridyl groups has been coordinated to Rh(I) and Ir(I) to give complexes of the type [M(κ(3)-1)(1,5-COD)]PF(6) (2 M = Rh; 3 M = Ir). In contrast to our earlier study with this ligand, the complexes have been shown to approximate to a trigonal bipyramidal geometry in the solid state and exist as an isomeric mixture in solution as determined by (1)H and (13)C NMR spectroscopy. Electrochemical studies revealed that both complexes undergo a 1-electron oxidation with the potential of the Rh complex 0.

Purification-free synthesis of a highly efficient ruthenium dye complex for dye-sensitised solar cells (DSSCs).

A novel Ru(II) sensitiser A597 containing the 4,4'-dioctylamido-2,2'-bipyridine ancillary ligand is synthesised without the need for purification steps. It shows an irreversible oxidation at 0.92 V in the cyclic voltammogram and an absorbtion at 539 nm in the UV-vis spectrum corresponding to an (1)MLCT transition.

Cu(I) complexes based on cis, cis-1,3,5-tris(arylideneamino)cyclohexane ligands: synthesis, structure and CO binding.

A new series of sterically bulky, facially coordinating N(3)-donor tach-based ligands (tach; cis,cis-1,3,5-triaminocyclohexane) [2.1; cis,cis-1,3,5-tris(2,4-dimethylbenzylideneamino)cyclohexane, 4.1; cis,cis-1,3,5-tris(pentamethylbenzylideneamino)cyclohexane, 5.

Homo- and heterodinuclear complexes of the tetrakis(pyrazolyl)borate ligand.

Monometallic complexes of the tetrakis(pyrazolyl)borate ligand [ML(2){B(pz)(4)}] {M = Rh, Ir; L(2) = eta-cod, eta-nbd, (CO)(2), (CO)(PPh(3))} have two free pyrazolyl rings which can be coordinated to a second ML(2) unit to give the dimeric compounds [L(2)M{mu-B(pz)(4)}ML(2)](+), and to a metal halide to give heterobimetallic species [L(2)M{mu-B(pz)(4)}M'Cl(2)]. (1)H NMR spectroscopy shows that [(eta-cod)Rh{mu-B(pz)(4)}Rh(eta-cod)](+) 1(+), [(eta-nbd)Rh{mu-B(pz)(4)}Rh(eta-nbd)](+) 2(+), [(eta-cod)Ir{mu-B(pz)(4)}Ir(eta-cod)](+) 3(+) and [(CO)(2)Rh{mu-B(pz)(4)}Rh(CO)(2)](+) 4(+) are fluxional at room temperature. Cooling a solution of [(eta-cod)Rh{mu-B(pz)(4)}Rh(eta-cod)](+) 1(+) to -90 degrees C slows the fluxional process, which involves inversion of the two B-(N-N)(2)-M six-membered rings.

Pandemic (H1N1) 2009 influenza vaccine roll-out in NSW.

The roll-out of the pandemic (H1N1) 2009 influenza vaccine in NSW was significantly different to that envisaged for a pandemic vaccination program. Pre-pandemic planning had focused on the urgent roll-out of a vaccine through mass vaccination clinics in a time of high demand due to a virulent influenza virus. Instead the situation was less urgent, with the vaccine available only after the peak of incidence of infections in NSW.

Luminescent, water-soluble gold nanoparticles functionalised with 3MLCT emitting rhenium complexes.

Rhenium complexes functionalised with thioester-terminated alkyl chains can be attached to gold nanoparticles to yield water-soluble, visibly luminescent Re-GNP hybrid conjugates.

Bonding modes, structures and fluxionality in rhodium and iridium tris(3,5-dimethylpyrazolyl)methane diene complexes.

The structures adopted by a range of hydrotris(3,5-dimethylpyrazolyl)methane complexes [ML(2){HC(pz')(3)}](+) (M = Rh, Ir; L(2) = diene) have been investigated. There is low steric hindrance between ligands in [Rh(eta-nbd){HC(pz')(3)}](+) (nbd = norbornadiene) and [Rh(eta-dmbd){HC(pz')(3)}](+) (dmbd = 2,3-dimethylbuta-1,3-diene) resulting in kappa(3) co-ordination of the pyrazolylmethane. The complexes [M(eta-cod){HC(pz')(3)}](+) (cod = cycloocta-1,5-diene) (M = Rh, Ir) are kappa(2) co-ordinated with the free pyrazolyl ring positioned above and approximately parallel to the square plane about rhodium or iridium.

Copper(I) complexes of cis,cis-1,3,5-tris(mesitylideneamino)cyclohexane ligands: synthesis, structure and substrate selectivity.

The new sterically encumbered facially coordinating N(3)-donor ligand cis,cis-1,3,5-tris(mesitylideneimino)cyclohexane (L1) has been synthesised. Reaction with [Cu(NCCH(3))(4)]PF(6) gives [Cu(L1)NCCH(3)]PF(6) (1), the bound acetonitrile being labile and readily replaced by CO to yield [Cu(L1)CO]PF(6) (2); both 1 and 2 have been structurally characterised. Complexes 1 and 2 do not undergo a substitution reaction with ethylene.

Continuous separation of racemic 3,5-dinitrobenzoyl-amino acids in a centrifugal contact separator with the aid of cinchona-based chiral host compounds.

Resolution through revolution: It is possible to extract 3,5-dinitrobenzoyl-protected amino acids enantioselectively with the aid of a table-top centrifugal contact separator and a catalytic amount of a chiral host compound based on the Cinchona alkaloids. Enantioselectivities of up to 80 % could be reached in a single pass. This allows the development of a process for the continuous separation of racemates.

Solid state and solution structures of rhodium and iridium poly(pyrazolyl)borate diene complexes.

The structures adopted by a range of poly(pyrazolyl)borate complexes [ML2Tp(x)] [M = Rh, Ir; L2 = diene; Tp(x) = Bp' {dihydrobis(3,5-dimethylpyrazolyl)borate}, Tp' {hydrotris(3,5-dimethylpyrazolyl)borate}, Tp {hydrotris(pyrazolyl)borate}, B(pz)4 {tetrakis(pyrazolyl)borate}] have been investigated. Low steric hindrance between ligands in [Rh(eta-nbd)Tp] (nbd = norbornadiene), [Rh(eta-cod)Tp] (cod = cycloocta-1,5-diene) and [Rh(eta-nbd)Tp'] results in K3 coordination of the pyrazolylborate but [M(eta-cod)Tp'] (M = Rh, Ir) are kappa2 coordinated with the free pyrazolyl ring positioned above and approximately parallel to the square plane about the metal. All but the most sterically hindered Tp(x) complexes undergo fast exchange of the coordinated and uncoordinated pyrazolyl rings on the NMR spectroscopic timescale.

Inter- versus Intramolecular C-H Activation: Synthesis and Characterization of a Novel Platinum-Carbene Complex.

C NMR spectroscopy as well as the short bond between the platinum and the C4 atom of the pyridine ring in 1 (1.95 Å) indicate the formation of a novel carbene species. Compound 1 is remarkably stable (m.