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Luminescent Electropolymerizable Ruthenium Complexes and Corresponding Conducting Metallopolymers
journal contribution
posted on 2018-10-09, 00:00 authored by Seyma Goren Keskin, Xunjin Zhu, Xiaoping Yang, Alan H. Cowley, Bradley J. HollidayTris(2,2′-bipyridyl)ruthenium(II)
dichloride [Ru(bpy)3Cl2] and analogous complexes
have been studied
extensively in the literature due to their luminescent and photochemical
properties as well as their excited-state lifetimes. Conducting polymers
with similar ruthenium groups have also been investigated for various
applications. In this study, syntheses of four ruthenium complexes
with a polymerizable tridentate ligand, bis[4-[2-(3,4-diethylenedioxy)thiophene]pyrazol-1-yl]pyridine
(EDOT2NNN), and with bidentate ligands, two of which were
anionic (hfac: 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; dbm: dibenzoylmethane)
and two of which were neutral (bpy: 2,2′-bipyridyl; phen: 1,10-phenanthroline),
were achieved for potential OLED/PLED applications. Saturated CH2Cl2 solutions of monomers were oxidatively and
electrochemically polymerized, and the scan rate dependences of the
polymers were measured. UV–vis spectroscopic characterizations
of the complexes and the EDOT-functionalized ligand were obtained.
[Ru(EDOT2NNN)(phen)(Cl)](PF6) was electropolymerized
on an ITO (indium tin oxide)-coated glass surface to obtain the solid-state
absorption spectrum of the corresponding polymer. Photophysical data
for each complex, i.e., excitation and emission spectra at 77 K and
RT, in EtOH/MeOH (4:1) and in 2-MeTHF (dry, air-free, and aerated),
quantum yield, and luminescence lifetime have been measured. The radiative
and nonradiative decay constants as well as the oxygen quenching rate
coefficient for each complex were calculated. [Ru(EDOT2NNN)(phen)(Cl)](PF6), having the highest quantum yield
of phosphorescence and the longest lifetime, was electropolymerized
on an ITO-coated glass surface to obtain the solid-state excitation
and emission spectra of the corresponding polymer. Luminescence studies
of the polymer had promising results for photoluminescence.
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RTNNNLuminescent Electropolymerizable Ruthenium ComplexesOLEDpolymerizable tridentate ligandConductingSaturated CH 2 Cl 2 solutionsemission spectraquantumnonradiative decay constantsUVscan rate dependencesoxygen quenching rate coefficientrutheniumITO-coated glass surfacelifetimeEDOTapplicationcomplexelectropolymerizedexcitation
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