Thesis--University of Wisconsin--Madison. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 373-379).

Thesis (M.S.)--Michigan State University. Geological Sciences, 2008. / Title from PDF t.p. (Proquest, viewed on Aug. 10, 2009) Includes bibliographical references (p. 87-90). Also issued in print.

Thesis (Ph. D.)--University of Delaware, 2009. / Principal faculty advisor: Svilen Bobev, Dept. of Chemistry and Biochemistry. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1983. / Typescript. Vita. Description based on print version record. Includes bibliographical references (leaves 160-166).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1981. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Luminescent lanthanide coordination complexes have attracted significant attention due to their unique optical properties. The poor absorption of a lanthanide ion can be resolved by so-called antenna effect and improve the intensity of its luminescence. Three bidentate chromophores: phosphate-pyridine chromophore, 1,2-Hydroxy pyridone (1,2-HOPO) and 2-thenoyltrifluoroacetone (TTA), functioned as both chelator and sensitizer, their energy levels are well matched with the excited state energy levels of the Eu(III) and Sm(III).. To get highly luminescent and stable lanthanide complex, we designed and synthesized various Eu(III) complexes with different backbones to compare different parameters that will affect the sensitizing efficiency of the chromophores, such as rigidity, geometry and coordination saturation.. In chapter two we combined the phosphate-pyridine chromophore with the well-studied cyclen-based chelator to fulfil the requirement of high stability and brightness. We designed a nine-coordinate europium(III) complex as platform, through coupling reactions to realise fast screen of the chromophores energy transfer efficiency.. Chapter three focuses on the structure modifications based on the chromophore of 1,2-HOPO, different chelators and backbones were compared, a europium complex EuL4 with the highest quantum yield with this chromophore was obtained and it could goes into cells and localized on lysosome very fast. Two-phonon in vitro imaging was done which showed its high potential bioapplications.. Chapter four focuses on the structure modification based on the chromophore of TTA. Different backbone directly determined the europium complexes saturation number and sensitization efficiency, therefore, their quantum yields.

The ligands di(2-pyridyl) ketone (DPK) and cis-1,2 di(2-pyridyl) ethylene (DPE) are N,N,Odonor ligands that can undergo nucleophilic addition and become more flexible for coordination. The reaction between the lanthanide thiocyanate salt and DPK gave rise to seven novel complexes of the general formula [Ln(NCS)3(DPKOH)3], where Ln = La, Ce, Nd, Eu, Tb, Dy and Ho. 1H NMR spectroscopy verified that the ligand underwent nucleophilic addition upon coordination. This was further confirmed using UV-Vis spectroscopy which showed a shift in the absorption bands due to conjugation of electrons within the pyridyl ring upon coordination. UV-Vis spectroscopy was also utilised to test the covalent character of the neodymium and holmium complexes. X-ray diffraction and IR spectroscopy showed that three DPK ligands coordinated bidentately through a pyridinic nitrogen and a hydroxyl oxygen, while three isothiocyanato molecules completed the coordination environment around each metal. Furthermore, X-ray diffraction also revealed that these complexes are isostructural, ninecoordinate and the polyhedron which encloses each ion is of trigonal tricapped prismatic shape with D3h symmetry. Micro-analysis on all the complexes, except lanthanum and holmium confirmed the molecular formulae produced from the crystallographic data of each complex. The reaction between the lanthanide thiocyanate salt and DPE produced poor quality crystals which could not be detected by X-ray diffraction. The lanthanide salts used for this reaction were lanthanum, neodymium, europium, dysprosium and holmium. Upon coordination, conductivity measurements detected the presence of lanthanide ions in each solution. 1H NMR and IR spectroscopic studies showed that the ethylenic moiety of DPE underwent nucleophilic addition upon coordination. UV-Vis spectroscopy further confirmed nucleophilic addition upon coordination due to shifts in absorption bands. IR spectroscopy verified the possibility of a bidentate coordination to each metal through a pyridinic nitrogen and a hydroxyl oxygen as well as a monodentate coordination through isothiocyanato ligands. A micro-analysis on all the complexes provided the molecular formulae that can best fit each complex. The effect of the solvent molecules on the bonding parameters of the lanthanum complex was investigated. An analysis of the results produced from crystallographic data revealed the presence of intermolecular forces which interacted and stabilised the complex.

This study investigates the coordination behaviour of potentially bi- and tridentate O,O- and O,N,O-donor Schiff base ligands with trivalent lanthanide ions. The reactions of lanthanide nitrates with 2-((E)-(tert-butylimino)methyl)-6-methoxyphenol (HL1) have yielded five complexes that are described by the general formula [Ln(HL1)2(NO3)3] (Ln = Ce, Nd, Gd, Ho and Er) and were characterised using physico-chemical techniques including single-crystal X-ray diffraction spectroscopy. The cerium complex crystallised in a triclinic (P-1) space group, while the rest of the complexes crystallised in the monoclinic (P21/c) space group. All the complexes are ten-coordinate adopting a tetradecahedron geometry with two HL1 molecules coordinated through the phenolic and methoxy oxygen atoms. The coordination sphere is completed by six oxygen atoms from three bidentately coordinated nitrate ligands. Electronic data reveals that only the neodymium, holmium and erbium complexes exhibit weak f-f transitions in the visible region. The redox behaviour of the complexes was also investigated and reported. Five novel complexes were prepared by reacting 2-((E)-(tert-butylimino)methyl)phenol (HL2) with [Ln(NO3)3∙xH2O] (Ln = Gd and Dy ; x = 5 or 6) and [LnCl3∙6H2O] (Ln = Nd, Gd and Dy). The crystal structures of the former two complexes are isostructural and the coordination sphere is composed of three HL2 ligands bonded to the metal centre through the phenolic oxygen atom and three nitrate ions coordinated in a bidentate fashion. Both complexes are nine-coordinate and SHAPE analysis reveals that they adopted a muffin geometry. The average Ln-Onitrate and Ln-Ophenolate bond lengths are 2.5078 and 2.2814 Å, respectively. The complexes derived from the chloride salts exhibited an octahedral geometry with four monodentate ligands [Ln-Ophenolate distances range from 2.224(4) to 2.2797(17) Å] coordinating in the equatorial positions and two chloride ions [average Ln-Cl bond length is 2.6527 Å, and average Cl-Ln-Cl angles is 180o] in axial positions. The ligand coordinated through the phenolic oxygen with the phenolic proton migrating to the imino nitrogen to give a zwitterionic form of the ligand. There are weak C-H∙∙∙Cl interactions present and O-H∙∙∙N hydrogen bonds are also observed in the crystal packing. The synthesis of lanthanide complexes with methoxy-6-((E)-(phenylimino)methyl)phenol (HL3) was carried out in methanol to yield two mononuclear complexes with the formulae [Nd(HL3)2(NO3)3] and [Ho(HL3)(NO3)3(DMF)(H2O)]. Single-crystal crystallographic studies shows that the neodymium complex contains two HL3 ligands coordinated bidentately through its methoxide and phenolic oxygen atoms, with three nitrate ions also bonded to the metal in a bidentate manner. The coordination geometry in the holmium complex is composed of only oxygen atoms from the various ligands. Both complexes are ten-coordinate and exhibit a tetradecahedron geometry.

The reactions of Ln(NO3)3∙6H2O (Ln = Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H2pydm) were investigated, and complexes with the formula, [Ln(H2pydm)2(NO3)2](NO3) (Ln = Pr or Nd) and [Er(H2pydm)3](NO3)3 were isolated. The ten-coordinate Pr(III) and Nd(III) compounds crystallise in the triclinic space group P-1 while the nine-coordinate Er(III) complex crystallises in the monoclinic system (P21/n). The reaction of PrCl3∙6H2O with H2pydm yielded the compound, [Pr(H2pydm)3](Cl)3, that crystallises in the monoclinic system, space group P21/c with α = 90, β = 98.680(1) and γ = 90°. The nine-coordinate Pr(III) ion is bound to three H2pydm ligands, with bond distances Pr-O 2.455(2)-2.478(2) Å and Pr-N 2.6355(19)-2.64(2) Å. X-ray crystal structures of all the H2pydm complexes reveal that the ligand coordinates tridentately, via the pyridyl nitrogen atom and the two hydroxyl oxygen atoms. The electronic absorption spectra of complexes show 4f-4f transitions. Rare-earth complexes, [Ln(H2L1)2(NO3)3] [Ln = Gd, Ho or Nd], were also prepared from a Schiff base. The X-ray single-crystal diffraction studies and SHAPE analyses of the Gd(III) and Ho(III) complexes shows that the complexes are ten-coordinate and exhibit distorted tetradecahedron geometries. With proton migration occurring from the phenol group to the imine function, complexation of the lanthanides to the ligand gives the ligand a zwitterionic phenoxo-iminium form. A phenolate oxygen-bridged dinuclear complex, [Ce2(H2L1)(ovan)3(NO3)3], has been obtained by reacting Ce(NO3)3∙6H2O with an o-vanillin derived Schiff base ligand, 2-((E)-(1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (H2L1). Hydrolysis of the Schiff base occurred to yield o-vanillin, which bridged two cerium atoms with the Ce∙∙∙Ce distance equal to 3.823 Å. The Ce(III) ions are both tencoordinate, but have different coordination environments, showing tetradecahedron and staggered dodecahedron geometries, respectively. The reaction of salicylaldehyde-N(4)-diethylthiosemicarbazone (H2L2) in the presence of hydrated Ln(III) nitrates led to the isolation of two novel compounds: (E)-2[(ortho-hydroxy)benzylidene]-2-(thiomethyl)-thionohydrazide (1) and bis[2,3-diaza4-(2-hydroxyphenyl)-1-thiomethyl-buta-1,3-diene]disulfide. The latter is a dimer of the former. For this asymmetric Schiff base, 1 and the symmetric disulfide, classical hydrogen bonds of the O–H∙∙∙N as well as N–H∙∙∙S (for 1) type are apparent next to C–H∙∙∙O contacts. 4-(4-Bromophenyl)-1-(propan-2-ylidene)thiosemicarbazide was also prepared upon reacting 4-(4-bromophenyl)-3-thiosemicarbazide with acetone in the presence of ethanol and La(NO3)3∙6H2O. The C=S bond length was found to be 1.6686(16) Å which is in good agreement with other thioketones whose metrical parameters have been deposited with the Cambridge Structural Database. Classical hydrogen bonds of the N–H∙∙∙N and the N–H∙∙∙Br type are observed next to C–H∙∙∙S contacts. All synthesised compounds were characterised by microanalyses, single-crystal X-ray diffraction (except for [Nd(H2L1)2(NO3)3]), 1H NMR and IR spectroscopy.

Designing hybrid materials allows leveraging the properties of different material systems to achieve novel functions. Significant progress has been made in recent years to exploit the physicochemical properties of a new generation of hybrid materials for emerging biomedical applications. In Chapter 1, I review the recent advances in the field of dye-lanthanide hybrid materials, centring on the interface between organic dyes and inorganic lanthanide materials and investigating their photophysical and photochemical properties. Five representative dye-lanthanide hybrid material systems including lanthanide complex, dye-sensitised downshifting nanoparticles (DSNPs), dye-sensitised downconversion nanoparticles (DCNPs), dye-sensitised upconversion nanoparticles (UCNPs), and UCNPs-dye energy transfer systems have been thoroughly discussed. We highlight the key applications of dye-lanthanide hybrid materials in bioimaging, sensing, drug delivery, therapy, and cellular activity studies. In Chapter 2, I design and synthesize an ytterbium complex-based sensor for the detection of Hg2+ ions. The water-soluble ytterbium complex exhibits reversible off−on visible and NIR emission upon the binding with mercury ion. The fast response and 150 nM sensitivity of Hg2+ detection are based upon FRET and the lanthanide antenna effect. The reversible Hg2+ detection can be performed in vitro, and the binding mechanism is studied by NMR employing the motif structure in a La complex and by DFT calculations. In Chapter 3, I report a pair of stoichiometric terbium-europium dyads as molecular thermometers and study their energy transfer properties. A strategy for synthesizing hetero-dinuclear complexes that contain chemically similar lanthanides is developed. By this strategy, a pair of thermosensitive dinuclear complexes, cycTb-phEu and cycEu-phTb, was synthesized. Their structures were geometrically optimized with an internuclear distance of approximately 10.6 Å. The dinuclear complexes have sensitive temperature-dependent luminescent intensity ratios of europium and terbium emission, and temporal dimension responses over a wide temperature range (50 - 298 K and 10 - 200 K, respectively). This indicates that both dinuclear complexes are excellent self-referencing thermometers. In Chapter 4, I investigate spectral structure and intensity changes of a pair of dinuclear complexes with a europium ion on cyclen site and a lanthanum ion on phen site or vice verses (cycEu-phLa and cycLa-phEu). Though they have the same components and the same energy levels, they present different photophysical properties due to the different coordination environment. The band positions are different in the emission spectra. The emission of cycEu-phLa showed a stronger relative intensity of 5D0 7F2 transition whereas the relative intensity of 5D0 7F4 transition was weaker in comparison with cycLa-phEu. We found the cycEu-phLa have higher internal quantum efficiency while the cycEu-phLa have higher sensitizing efficiency, though they have similar external quantum yield. We determined the singlet-triplet intersystem crossing rate with values as ~108 s-1. In Chapter 5, I exploit a dye sensitised upconversion nanoparticle with highly enhanced upconversion emission. I designed and synthesized a new dye by connecting tetraphenylethene (TPE) with the cyanide NIR dye, IR783. The resultant compound (TPEO-IR783) has a quantum yield of 22.46% which is 3 times higher than that of reported UCNP sensitiser (IR806). The TPEO-IR783 exhibits a transparent window in a range of 400 nm to 600 nm, making it suitable sensitiser for upconversion nanoparticles by avoiding reabsorption. The TPEO-IR783 sensitised UCNPs show more than 200-fold upconversion emission than the reported IR806 sensitised UCNPs under the same condition. In Chapter 6, I develop an ytterbium nanoparticle-mediated upconversion system. The system enables the singlet energy transfer from sensitisers to acceptor triplet states without the requirement of intersystem crossing. I evaluate the hybrid upconversion design by IR808 and rubrene acid. While the mixture of IR808 and rubrene acid does not show any upconversion emission, the introduction of an intermediate ytterbium energy level by adding NaGdF4:Yb nanoparticles displays strongly enhanced upconversion emissions. This design bypasses the specific requirement of traditional sensitisers in TTA system, providing a wide range of opportunities in deep tissue applications. Chapter 7 is the experiment sections where details of materials, characterizations, and synthetic procedures in each chapter have been provided.