Transition Metal Complexes Anchored on Europium Oxide Nanoparticles
Zapiter, Joan Marie Diangson
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Polypyridyl transition metal complexes containing ruthenium, rhodium and iridium centers are mainly studied due to their light absorbing and emitting properties. Lanthanide oxides such as europium oxide absorb light as well and exhibit strong luminescence and long lifetimes. The optical properties of these materials were significant especially in solar energy utilization schemes and optical applications. Energy transfer across a surface is important in several applications including phosphors and biomedical applications. Excited states of metal complexes with a carboxylate-containing ligand such as deeb = diethyl-2,2'-bipyridine-4,4'-dicarboxylate were studied on nanoparticle surfaces. In this work, [Rh(deeb)2Cl2](PF6), [Ir(deeb)2Cl2](PF6) and [Ir(deeb)2(dpp)](PF6)3 were synthesized using the building block approach. The metal complexes were characterized using 1H NMR spectroscopy, mass spectrometry, electronic absorption spectroscopy and electrochemistry. The 1H NMR spectra of the complexes were consistent with those of their ruthenium analogs. Mass spectra contain fragmentation patterns of the (M-PF6)+ molecular ion for [Rh(deeb)2Cl2](PF6) and [Ir(deeb)2Cl2](PF6), and (M-3PF6)3+ molecular ions for [Ir(deeb)2(dpp)](PF6)3. The electronic absorption spectrum of [Rh(deeb)2Cl2](PF6) shows a maximum at 328 nm, which is assigned as 1π→π*transition. The electronic absorption spectrum of [Ir(deeb)2Cl2](PF6) shows maxima at 308 nm and 402 nm, which are assigned as 1π→π* and metal-to-ligand charge transfer transitions, respectively. The [Ir(deeb)2(dpp)](PF6)3 complex exhibits peaks due to 1π→π* transitions at 322 nm and 334 nm. [Rh(deeb)2Cl2](PF6) has emission maxima from the 3LF state at 680 nm and 704 nm for the solid and glassy solutions at 77 K, respectively. [Ir(deeb)2Cl2](PF6) has emission maxima from the 3MLCT state at 538 nm in acetonitrile and 567 nm in the solid state at room temperature, with lifetimes of 1.71 μs and 0.35 μs, respectively. [Ir(deeb)2Cl2](PF6) has an unusually higher quantum yield than analogous compounds. [Ir(deeb)2(dpp)](PF6)3 has emission maxima from the 3IL state at 540 nm in acetonitrile and 599 nm in the solid state at room temperature, with lifetimes of 1.23 μs and 0.14 μs, respectively. Cyclic voltammetry of [Ir(deeb)2Cl2](PF6) and [Ir(deeb)2(dpp)](PF6)3 yield reversible and quasi-reversible couples corresponding to deeb ligand and Ir3+/+reductions, respectively. Attachment of the complexes were conducted by equilibration of complex solutions in acetonitrile with europium oxide nanoparticles. Europium oxide nanoparticles, which were synthesized by gas-phase condensation, have 11-nm diameters and exhibit sharp f-based luminescence in the visible and near IR regions. EDX, TEM, IR and reflectance spectroscopy measurements indicate substantial coating through various modes of attachment of the nanoparticle surface by the metal complexes while retaining the excited state properties of the metal complexes. Surface adsorption studies indicate monolayer coverage of the nanoparticle surface by the metal complexes, consistent with limiting surface coverages of previously reported analogous systems. Eu2O3 nanoparticles modified with [Rh(deeb)2Cl2]+ exhibit minimal to no energy transfer from emission spectra, and a reduction in the lifetime at 77K could be due to the rhodium complex preventing the excitation of Eu3+. Upon attachment of the Ir complexes [Ir(deeb)2Cl2]+ and [Ir(deeb)2(dpp)]3+ on as-prepared nanoparticles, Eu3+ luminescence was observed for nanoparticles modified with iridium complexes at room temperature, which could be due to energy transfer among other possibilities. Efficiencies of 68% and 50%, and energy transfer rate constants of 1.1 x 10-5 and 1.0 x 10-5 were calculated from lifetime data for [Ir(deeb)2Cl2]+ and [Ir(deeb)2(dpp)]3+ on Eu2O3 nanoparticles, respectively. Since iridium complexes are used as components of light-emitting diodes, europium oxide nanoparticles modified with iridium complexes have potential in optical applications which make studies of these compounds interesting.
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