Luminescent lanthanide complexes have been widely studied for various biotechnology and materials science uses, however, the application of these luminescent systems in metallopolymers has been relatively limited, especially when compared to those incorporating transition metal complexes. The unique and interesting photophysical properties of lanthanide complexes (i.e., high color purity and long radiative lifetimes) make these systems ideal for the development of luminescent metallopolymers, which are a unique class of hybrid materials that synthetically incorporate metal centers into organic polymers, thereby taking advantage of the beneficial properties of both traditional inorganic (i.e., catalysis, optics, electronics) and organic (i.e., easy to process, flexible, low weight) materials. A new class of lanthanide complexes exhibiting metal-based visible and near-IR photoluminescence has been designed, synthesized and fully characterized by melting point, ESI-MS, elemental analysis and single crystal and powder X-ray diffraction (when possible). The photophysical properties of these luminescent monomer complexes were studied in solution and the solid state, with the emission spectra displaying the characteristic line-like emission peaks of the trivalent lanthanide ions. This indicates efficient energy transfer from ligand centered excited states to the emissive excited states of the lanthanides. The monomer complexes have been electropolymerized, resulting in conducting metallopolymers that display metal-based photoluminescence. Because these hybrid materials retain the desirable properties of both inorganic semiconductors and organic polymers, such as near metallic electrical conductivity, ease of processing, flexibility and light weight, they are promising for applications in solid-state lighting. / text

Conducting polymers that contain metals are remarkable materials, because they have the properties of both organic backbones and metals. Depending on the position of the metal relative to the conjugated backbone, i.e. attached to or directly in the backbone, these two can couple resulting in advancement of the functionality and therefore potential applications of these types of materials. Complexes of tridentate ligands with donor atoms such as phosphorus, nitrogen, and sulfur also have a wide variety of applications. In addition, complexes of tridentate ligands have advantages of stability and control of electron density by variation of donor atoms. Therefore, conjugated polymers with tridentate ligand units will have promise for various applications and advantages in their designs. Complexes of PNP ligand with molybdenum and carbonyl ancillary ligands were synthesized and characterized. Isomerization and conversion reactions between them were investigated as well as the coordination modes. Many types of PNP ligands have been studied in the literature because the hemilabile property of the nitrogen atom promotes some catalytic reactions and gives different coordination geometries. Conducting polymers can be used as redox-active ligands and they can be used to control electron density on the metal attached to them. Synthesis and characterization of a novel polymerizable ligand 3,5-bis-EDOT-N,N-bis[2-diphenylphosphinoethyl]aniline was achieved. Related molybdenum complexes with ancillary ligands as carbonyls were also synthesized and characterized. Monomer complexes and the free ligand were electropolymerized and studied. Tris(bipyridine)ruthenium(II) chloride and analogous complexes have been studied extensively in the literature due to their luminescent and photochemical properties, and excited state lifetimes. Conducting polymers with similar ruthenium groups have been investigated for various applications. Synthesis of four ruthenium complexes with the polymerizable ligand 2,6-Bis[4-[2-(3,4-diethylenedioxy)thiophene]pyrazol-1-yl]pyridine and four different bidentate ligands were reproduced; electropolymerizations of the complexes were achieved; electrochemical, UV-Vis and luminescence studies were performed and discussed. Various complexes of copper, silver, platinum, and palladium with nitrogen and phosphorus donors have been reported for their luminescence behavior as well as their interesting structures. Model complexes of these metals with N,N-bis[2-(diphenylphosphino)ethyl]phenyl-amine (a PNP ligand) have been synthesized and characterized. Absorption and luminescence behaviors as well as the coordination modes were investigated. / text

Conducting metallopolymers possess attractive electronic properties for use in sensors, photoelectronic devices, catalysts, and other applications. Modification of the conducting polymer backbone, through chemical or electrochemical methods, enables control of catalytic, electronic, and optical properties of the metal via inductive modulation of the electron density. Understanding in detail the relationship between the metal and polymer backbone could lead to more effective metallopolymer materials. We hope to study this relationship by probing the band gaps, excited state energy levels, catalytic activity, and sensor function in four metallopolymer systems. Devices with sub-stochiometric ratios of Cu2ZnSnS4 NPs (CZTS: (Cu2Sn)1-xZn1/xS)(0≥x≥0.75)) grown in Cu(II) conducting metallopolymers were produced to study band gap tuning in hybrid materials. The valence and conductance bands of CZTS (x = 0.60) aligned with the HOMO/LUMO of the Cu(II) metallopolymer. Changing the alignment facilitated charge transfer in the hybrid material, leading to photovoltaic materials with efficiencies of ~0.1%. Chemoresistive ionophore sensors were developed by incorporating selective binding groups, such as thiourea, into conducting polymer backbones. Thiourea monomers and polymers showed high selectivity for Pb(II) ions over many competitive ions. XPS experiments demonstrated that reversible chelation of Pb(II) ions could be achieved through a simple uptake/rinse process. The conductivity of the thiourea polymer increased fifty-fold, from 7.75×10−2 S/cm2 to 3.5 S/cm2, after Pb(II) exposure. Sensitivity measurements indicated the sensors have limits of detection near 10−10 M. Highly conjugated ligands were synthesized to explore effective sensitization of visible and near-IR emitting lanthanides. (3,4-ethylenedioxy)thiophene was appended to dipyridophenazine and dipyridoquinoxaline to introduce a group that could be easily electropolymerized. These bi-functional ligands emitted from π-π* and an inter-ligand charge transfer excited states, and therefore, two distinct triplet states were observed. These separate energy pathways allowed for efficient sensitization of both visible (Tb(III), Eu(III), Dy(III)) and near-IR emitting (Nd(III), Yb(III), Er(III)) ions. Finally, we explored the oxidation of a rhodium-containing conducting metallopolymer and the subsequent effect on the activity of the metal center. Oxidation of the backbone led to ancillary ligand attenuation, allowing for control of the catalytically active species in the conducting metallopolymer. Rh(I,III) monomer and metallopolymer catalytic studies showed potential for new heterogenous/homogeneous hybrid catalysts. / text