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Morpholine motifs have been used extensively as targeting moieties for lysosomes, primarily in fluorescence imaging agents. Traditionally these imaging agents are based on organic molecules which have several shortcomings including small Stokes shifts, short emission lifetimes, and susceptibility to photobleaching. To explore alternative lysosome targeting imaging agents we have used a rhenium based phosphorescent platform which has been previously demonstrated to have an improved Stokes shift, a long lifetime emission, and is highly photostable. Rhenium complexes containing morpholine substituted ligands were designed to accumulate in acidic compartments. Two of the three complexes prepared exhibited bright emission in cells, when incubated at low concentrations (20 μM) and were non-toxic at concentrations as high as 100 μM, making them suitable for live cell imaging. We show that the rhenium complexes are amenable to chemical modification and that the morpholine targeted derivatives can be used for live cell confocal fluorescence imaging of endosomes-lysosomes.

Functionalising organic molecular photoswitches with metal complexes has been shown to alter and enhance their switching states. These organometallic photoswitches provide a promising basis for novel smart molecular materials and molecular electronic devices. We have detailed the synthesis and characterisation of mono- and bimetallic half-sandwich ruthenium and iron complexes functionalised with alkynyl dihydropyrenes (DHP). Their electronic and photophysical properties were determined by the use of chemical, electrochemical and spectroelectrochemical techniques. The introduction of the metal alkynyl moiety allows access to additional redox and protonation states not accessible by the DHP alone. An additional metal alkynyl moiety inhibits observable photochromic switching. Analysis of the NIR and IR bands in the mixed valence complexes suggests there is a high degree of charge delocalisation across the DHP.

Three new NiII/ZnII heterometallics, [NiZnL'2(OMe)Cl]2 (1), [NiZnL''(Dea)Cl]2·2DMF (2) and [Ni2(H3L''')2(o-Van)(MeOH)2]Cl·[ZnCl2(H4L''')(MeOH)]·2MeOH (3), containing three-dentate Schiff bases as well as methanol or diethanolamine (H2Dea) or o-vanillin (o-VanH), all deprotonated, as bridging ligands were synthesized and structurally characterized. The Schiff base ligands were produced in situ from o-VanH and CH3NH2 (HL'), or NH2OH (HL"), or 2-amino-2-hydroxymethyl-propane-1,3-diol (H4L'''); a zerovalent metal (Ni and Zn in 1, Zn only in 2 and 3) was employed as a source of metal ions. The first two complexes are dimers with a Ni2Zn2O6 central core, while the third compound is a novel heterometallic cocrystal salt solvate built of a neutral zwitterionic ZnII Schiff base complex and of ionic salt containing dinuclear NiII complex cations. The crystal structures contain either centrosymmetric (1 and 2) or non-symmetric di-nickel fragment (3) with NiNi distances in the range 3.146-3.33 Å. The exchange coupling is antiferromagnetic for 1, J = 7.7 cm-1, and ferromagnetic for 2, J = -6.5 cm-1 (using the exchange Hamiltonian in a form Ĥ = Jŝ1ŝ2). The exchange interactions in 1 and 2 are comparable to the zero-field splitting (ZFS). High-field EPR revealed moderate magnetic anisotropy of opposite signs: D = 2.27 cm-1, E = 0.243 cm-1 (1) and D = -4.491 cm-1, E = -0.684 cm-1 (2). Compound 3 stands alone with very weak ferromagnetism (J = -0.6 cm-1) and much stronger magnetic anisotropy with D = -11.398 cm-1 and E = -1.151 cm-1. Attempts to calculate theoretically the exchange coupling (using the DFT "broken symmetry" method) and ZFS parameters (with the ab initio CASSCF method) were successful in predicting the trends of J and D among the three complexes, while the quantitative results were less good for 1 and 3.

Trinuclear lanthanoid clusters have been synthesised and investigated as toroidal spin systems. A pyridyl functionalised β-diketonate, 1,3-bis(pyridin-2-yl)propane-1,3-dione (o-dppdH) has been used to synthesise a family of clusters of the form [Dy3(OH)2(o-dppd)3Cl2(H2O)4]Cl2·7H2O (1), [Tb3(o-dppd)3(μ3-OH)2(CH3CH2OH)3Cl3][Tb3(o-dppd)3(μ3-OH)2(H2O)(CH3CH2OH)2Cl3]Cl2·H2O (2), [Ho3(OH)2(o-dppd)3Cl(H2O)5]Cl3·3H2O (3) and [Er3(OH)2(o-dppd)3Cl2(H2O)3(CH3OH)]Cl2·3H2O·CH3OH (4). Despite the previous occurrence of this structural motif in the literature, these systems have not been widely investigated in terms of torodic behaviour. Magnetic studies were used to further characterise the complexes. DC susceptibility studies support weak antiferromagnetic exchange in the complexes. Slow magnetic relaxation behaviour is observed in the dynamic AC magnetic studies for complex 1. Theoretical studies predict that complex 1 and 3 have a non-magnetic ground state based on a toroidal arrangement of spins. Changes to the coordination environment in 2 do not support a toroic spin state. The prolate nature of the ErIII centres in complex 4 and large transverse anisotropy do not support the toroidal arrangement of lanthanoid spins in the complex.

The synthesis of a novel Rh(i)-aryl complex is detailed and its ability to serve as an initiator in the stereospecific polymerisation of phenylacetylene evaluated. Targeting the Rh(i) species, (2-phenylnaphthalen-1-yl)rhodium(i)(2,5-norbornadiene)tris(para-fluorophenylphosphine), Rh(nbd)(P(4-FC 6 H 4 ) 3 )(2-PhNapth), following recrystallization we obtained the isomeric (2-(naphthalen-2-yl)phenyl)rhodium(i) complex, Rh(nbd)(P(4-FC 6 H 4 ) 3 )(2-NapthPh), as determined by X-ray single-crystal structure analysis, and confirmed by X-ray powder diffraction. The isolation of the latter species was proposed to occur from the target (2-PhNapth) derivative via an intramolecular 1,4-Rh atom migration. This supposition was supported by density functional theory (DFT) calculations that indicated the isolated (2-NapthPh) derivative has lower energy (-19 kJ mol -1 ) than the targeted complex. The structure of the isolated (2-NapthPh) species was confirmed by multinuclear NMR spectroscopy including 2D 31 P- 103 Rh{ 1 H, 103 Rh}, heteronuclear multiple-quantum correlation (HMQC) experiments; however, NMR analysis indicated the presence of a second, minor species in solution in an approximate 1 : 4 ratio with the 2-NapthPh complex. The minor species was identified as a second structural isomer, the 3-phenylnaphthyl derivative, proposed to be formed under a dynamic equilibrium with the 2-NapthPh derivative via a second 1,4-Rh atom migration. DFT calculations indicate that this 1,4-migration proceeds through a low-energy pathway involved in the oxidative addition of a C-H bond to Rh followed by a reductive elimination with the distribution of the products being thermodynamically controlled. The recrystallized Rh(nbd)(P(4-FC 6 H 4 ) 3 )(2-NapthPh) complex was subsequently evaluated as an initiator in the polymerisation of phenylacetylene (PA); gratifyingly, the Rh(i) species was an active initiating species with the pseudo-first-order kinetic and molecular weight evolution vs time plots both linear implying a controlled polymerisation while yielding (co)polymers with low dispersities (Đ = M w /M n typically ≤1.25) and high cis-transoidal stereoregularity (>95%). Typical initiation efficiencies, while not quantitative (as judged by size exclusion chromatography), were nonetheless high at ca. 0.8. The presence of the minor 3-phenylnaphthyl species when in solution is proposed to be the cause of the observed non-quantitative initiation.

The synthesis, structural and photophysical characterisation of four tricarbonyl rhenium(i) complexes bound to 1,10-phenanthroline and a tetrazolato ancillary ligand are reported. The complexes are differentiated by the nature (hydroxy or methoxy) and position (meta or para) of the substituent attached to the phenyl ring in conjugation to the tetrazole ring. The complexes exhibit phosphorescence emission from triplet charge transfer excited states, with the maxima around 600 nm, excited state lifetime decays in the 200-300 ns range, and quantum yield values of 4-6% in degassed acetonitrile solutions. The nature and position of the substituent does not significantly affect the photophysical properties, which remain unchanged even after deprotonation of the hydroxide group on the phenol ring. The interpretation of the photophysical data was further validated by resonance Raman spectroscopy and time-dependent density functional theory calculations. All the complexes are internalised within cells, albeit to variable degrees. As highlighted by a combination of flow cytometry and confocal microscopy, the species display diffuse cytoplasmic localisation except for the complex with the hydroxy functional group at the para position, which reveals lower accumulation in cells and more pronounced punctate staining. Overall, the complexes displayed low levels of cytotoxicity.

A conjugated β-triketone, tris(2-naphthoyl)methane (tnmH), has been synthesized and successfully utilized as an antenna moiety for sensitization of the trivalent lanthanoids Eu3+, Sm3+, Yb3+ and Nd3+, in an isomorphous series of mononuclear complexes formulated as [Ln(tnm)3(DMSO)2] (Ln3+ = Nd3+, Sm3+, Eu3+, Gd3+ and Yb3+). The photophysical properties of the materials were characterized as comprehensively as possible, with overall quantum yields, intrinsic quantum yields based on calculated radiative decays, and sensitization efficiencies reported. This investigation improves understanding of the sensitization processes occurring in the near-infrared (NIR) region, where quantitative data are currently scarce. In fact, the [Yb(tnm)3(DMSO)2] and its deuterated analogue, [Yb(tnm)3(d6-DMSO)2], present high values of overall quantum yield of 4% and 6%, respectively, which makes them useful and readily accessible references for future investigation of NIR-emitting systems.

β-Triketonates have been recently used as chelating ligands for lanthanoid ions, presenting unique structures varying from polynuclear assemblies to polymers. In an effort to overcome low solubility of the complexes of tribenzoylmethane, four β-triketones with higher lipophilicity were synthesised. Complexation reactions were performed for each of these molecules using different alkaline bases in alcoholic media. X-ray diffraction studies suggested that the ligands were undergoing decomposition under the reaction conditions. This is proposed to be caused by in situ retro-Claisen condensation reactions, consistent with two examples that have been reported previously. The lability of the lanthanoid cations in the presence of a varying set of potential ligands gave rise to structures where one, two, or three of the molecules involved in the retro-Claisen condensation reaction were linked to the lanthanoid centres. These results, along with measurements of ligand decomposition in the presence of base alone, suggest the solvent used will modulate the impact of the retro-Claisen condensation in these complexes.

Isomorphous β-triketonate-based lanthanoid polymers containing tris(4-methylbenzoyl)methanide (mtbm) and Rb+ with formula {[Ln(Rb)(mtbm)4]2}n (Ln = Eu3+ and Nd3+) have been synthesised and structurally characterised. The photophysical properties for the Nd3+ complex presented relatively long lifetimes and high quantum yields in comparison with analogous β-diketonate complexes. Mixed lanthanoid complexes were also formed and their luminescence properties studied, with effective sensitisation of the 4F3/2 of Nd3+via the 5D0 of Eu3+, which is to the best of our knowledge the first example of Eu3+ to Nd3+ sensitisation in a structurally defined coordination complex or polymer.

An isomorphous series of lanthanoid complexes containing tribenzoylmethanide (tbm) and 1,10-phenanthroline (phen) ligands has been synthesised and structurally characterised. These complexes, formulated as [Ln(phen)(tbm)3] (Ln = Eu3+, Er3+ and Yb3+), were compared with analogous dibenzoylmethanide (dbm) [Ln(phen)(dbm)3] complexes to investigate the effect of changing β-diketonate to β-triketonate ligands on the photophysical properties of the complex. The photophysical properties for the Eu3+ complexes were similar for both systems, whereas a modest enhancement was observed for Yb3+ and Er3+ moving from the dbm to the tbm complexes. A detailed study of the NIR photophysical properties was achieved by adapting the integrating sphere method for the calculation of overall quantum yields in the solid state.

This paper describes the facile synthesis of a number of electron rich octamethyl[1.4]ferrocenophanes with unsaturated handles from 1,1'-bis(1-chlorovinyl)octamethylferrocene. Treatment of this reactive compound with sodium hydroxide in DMF initiates a series of reactions resulting in the formation of four different ferrocenophanes. The most complex of these products arises from a cascade of cyclisations giving an unusual, unsymmetrical bis-ferrocenophane with a central fused cyclobutene. Control over the reaction outcome is achieved by manipulating the concentration of NaOH. Mechanisms are proposed, and supported by DFT calculations.

Two new N-heterocyclic carbene (NHC) ligands bearing 2-morpholino and 2-piperidinyl naphthyl wingtips were synthesised (2-SIMorNap and 2-SIPipNap). Nuclear magnetic resonance studies, in conjunction with crystal structures and derivatisation of the NHC salts using a chiral counteranion, revealed that the ligand wingtips are oriented anti with respect to each other. From the free carbene, palladium, ruthenium and iridium complexes were prepared. NHC-iridium dicarbonyl complexes were made in order to extract the TEP values for these ligands. The study showed that these NHC ligands are more electron-donating than normal, aryl-substituted NHCs. The palladium complexes were tested in representative Suzuki-Miyaura cross-coupling reactions and compared to the state of the art systems. Ruthenium-catalysed ring-closing metathesis with these ligands was also performed. It was found that Grubbs' 2 nd generation catalyst incorporating 2-SIPipNap did not initiate at room temperature and required heating for RCM to occur.

Adducts of a number of tertiary pnicogen ligands ER(3) (triphenyl-phosphine and -arsine (PPh(3),AsPh(3)), diphenyl,2-pyridylphosphine (PPh(2)py), tris(4-fluorophenyl)phosphine (P(C(6)H(4)-4F)(3)), tris(2-tolyl)phosphine (P(o-tol)(3)), tris(cyclohexyl)phosphine (PCy(3))), with silver(I) thiocyanate, AgSCN are structurally and spectroscopically characterized. The 1:3 AgSCN : ER(3) complexes structurally defined (for PPh(3),AsPh(3) (diversely solvated)) take the form [(R(3)E)(3)AgX], the thiocyanate X = NCS being N-bound, thus [(Ph(3)E)Ag(NCS)]. A 1:2 complex with PPh(2)py, takes the binuclear form [(pyPh(2)P)(2)Ag()Ag(PPh(2)py)(2)] with an eight-membered cyclic core. 1:1 complexes are defined with PPh(2)py, P(o-tol)(3) and PCy(3); binuclear forms [(R(3)P)Ag()Ag(PR(3))] are obtained with P(o-tol)(3) (two polymorphs), while novel isomeric tetranuclear forms, which may be envisaged as dimers of dimers, are obtained with PPh(2)py, and, as further polymorphs, with PCy(3); these latter may be considered as extensions of the 'cubane' and 'step' forms previously described for [(R(3)E)AgX](4) (X = halide) complexes. Solvent-assisted mechanochemical or solvent-assisted solid-state synthesis methods were employed in some cases, where complexes could not be obtained by conventional solution methods, or where such methods yielded a mixture of polymorphs unsuitable for solid-state spectroscopy. The wavenumbers of the ν(CN) bands in the IR spectra are in broad agreement with the empirical rule that distinguishes bridging from terminal bonding, but exceptions occur for compounds that have a double SCN bridged dimeric structure, and replacement of PPh(3) with PPh(2)py apparently causes a significant decrease in ν(CN) to well below the range expected for bridging SCN in these structures. (31)P CP MAS NMR spectra yield additional parameters that allow a correlation between the structures and spectra.

Reaction of imidazole aldehydes with dihydrazino derivatives of 2-phenylpyrimidine provides a family of bis(acylhydrazone) ligands which form [2 × 2] metallogrid complexes with transition metal ions including Fe(II), Co(II), Cu(II) and Zn(II). The free ligands show H-bonding interactions, both donor and acceptor, largely involving the imidazole units, while binding of the metal ions occupies all the acceptor sites and leaves only the pyrrolic-NH site as an H-bond donor, although its deprotonation by a strong base can regenerate an acceptor. These H-bonding interactions have been studied by (1)H NMR spectroscopy in solution and in the solid state by means of several crystal structure determinations. The Fe(II) grids appear to be exclusively high-spin species over a wide temperature range in solution. In the solid state various forms of spin-crossover behaviour can be observed between 1.8 and 300 K, which has been rationalised in terms of the varied forms of hydrogen-bonding possible in the crystalline state.

An unsymmetrical bis(tridentate) ligand LH in which one binding site can be readily deprotonated forms a kinetically inert [Co(III)L(2)](+) complex which can be used as a "corner" species for the "Coupe du Roi" assembly of trans,trans-[Co(2)M(2)L(4)](6+) metallogrids (M = Fe(II), Co(II), Cu(II), Zn(II)). In the mixed Co(III)/Co(II) species, the oxidation states appear to be localised. In solution, the ligand LH forms octacationic, homometallic [2 × 2] grids with the individual labile metal ions Fe(II), Co(II), Cu(II), Zn(II), seemingly as mixtures of all possible isomers arising from the unsymmetrical nature of the ligand. In the solid state, however, [Zn(4)L(4)](CF(3)SO(3))(8)·4CH(3)CN crystallises as a single species where the cation has S(4) symmetry. This stereoselectivity in the crystalline lattice is associated with interactions between the cation and triflate anions which can again be analysed in terms of the Coupe du Roi concept.

Co(III) sarcophagine-type cage molecules, [Co(diCLsar)](3+) or [Co(HONOsar)](3+), form either 1 : 1 or 1 : 2 host-guest inclusion complexes with mono-phosphonium cations and sodium p-sulfonatocalix[4]arene in the solid state yielding complex I [p-sulfonatocalix[4]arene·Co(diCLsar)·2{benzyltriphenylphosphonium}], complex II [2{p-sulfonatocalix[4]arene}·Co(diCLsar)·3{tetraphenylphosphonium}] and complex III [p-sulfonatocalix[4]arene·Co(HONOsar)·tetraphenylphosphonium]. The diversity of the structural types of these multi-component systems, including the orientation of the Co(III) molecules in the cavities of the calixarenes, depends on the nature of their terminal functional groups. The secondary coordination interactions binding between the Co(III) molecules and p-sulfonatocalix[4]arene have also been investigated in water using NMR techniques.

In extension of recent synthetic and crystallographic studies of adducts of silver(I) oxyanion salts with uni- and bi-dentate nitrogen-donor ligands, AgX : L (1 : n), a parallel series of complexes formed with silver(I) trifluoromethanesulfonate ('tfs', 'triflate') has been similarly defined, showing rather more divergence from tendencies established with the previous ClO(4), NO(3), F(3)CCO(2) core arrays than might be expected from basicity arguments. Thus, while silver triflate crystallised from neat base forms 1 : 2 mononuclear adducts with 2,4,6-trimethylpyridine and quinoline which comprise essentially linear two-coordinate [LAgL](+) cations, perturbed by approaches of the anions, 1 : 2 adducts obtained similarly from pyridine and 2-methylpyridine are [L(2)Ag(mu-tfs)(2)AgL(2)] dimers, with central four- and eight-membered rings arising from mu-OSO(2)CF(3) and extended mu-(O,O'SOCF(3)) anion bridging modes, respectively. With piperidine, a single-stranded polymer reminiscent of the arrays [(pip)(2)AgX](infinity/infinity), X = Cl, NCS, is formed, the triflate bridging through two of its oxygen atoms, rather than via a single atom bridge. With 2- and 4-cyanopyridine, the former a 1 : 1 adduct (being an acetonitrile solvate (MeCN coordinated)), and the latter 1 : 2, both are more complex structures in which the nitrile functionalities now coordinate weakly. The 1 : 2 adduct with 2-acetylpyridine parallels its perchlorate analogue, the ligands being bidentate in a mononuclear complex [L(2)AgOSO(2)CF(3)], while adducts of 2,9-dimethylphenanthroline and 2,2'-biquinolyl, both acetonitrile monosolvates, take the form [LAg(NCMe)]tfs. Agtfs : dpk (8 : 8)(infinity/infinity).EtOH ('dpk' = bis(2-pyridyl)ketone) is a complex polymer. The nature of the interactions is explored by way of spectroscopy (IR, NMR and ESI MS) and a density functional theory approach.

The inclusion of o-carborane by p-Bu(t)-calix[7,9]arenes has been investigated by solid state and solution studies, with both resulting complexes in the solid state being rich in carborane with the ratio of calixarene to carborane at 1 : 7 and 2 : 7 respectively. The carboranes reside in clefts within the calixarenes which arise from specific local conformations of adjacent phenolic groups, or are included in the extended structure through other interplay of the calixarenes and carboranes in such clefts.

p-Bu(t)-calix[5]arene forms crystalline inclusion complexes with o- and m-carboranes in toluene or dichloromethane-hexane, but not with the p-isomer, the extended structures being based on 1 : 1 host-guest supermolecules, with the p-Bu(t)-substituents creating a snug fit for o- and m-carborane; p-carborane forms a highly hexane soluble complex, induced by grinding, which crystallizes as fibres. Solution phase studies showed the presence of a 1 : 1 host-guest stoichiometry with all three isomeric carboranes as determined from Job plots. The association constants for the o- and m-carborane complexes are 6.4 +/- 0.3 M(-1) and 3.8 +/- 0.1 M(-1) respectively, whereas the p-isomer is only weakly associated. Competition experiments involving all three isomers show rapid exchange on the NMR time scale, and no selectivity in solution is evident. Selective association involving the o- and m-isomers in the solid state is therefore remarkable, and it is a manifestation of crystal packing forces which embodies the differences in dipole moments of the carboranes.