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Synthesis and photophysical and electrochemical properties of functionalized mono-, bis-, and trisanthracenyl bridged Ru(II) bis(2,2':6',2"-terpyridine) charge transfer complexes.

ABSTRACT: With the aim of developing new molecular devices having long-range electron transfer in artificial systems and as photosensitizers, a series of homoleptic ruthenium(II) bisterpyridine complexes bearing one to three anthracenyl units sandwiched between terpyridine and 2-methyl-2-butenoic acid group are synthesized and characterized. The complexes formulated as bis-4'-(9-monoanthracenyl-10-(2-methyl-2-butenoic acid) terpyridyl) ruthenium(II) bis(hexafluorophosphate) (RBT1), bis-4'-(9-dianthracenyl-10-(2-methyl-2-butenoic acid) terpyridyl) ruthenium(II) bis(hexafluorophosphate) (RBT2), and bis-4'-(9-trianthracenyl-10-(2-methyl-2-butenoic acid) terpyridyl) ruthenium(II) bis(hexafluorophosphate) (RBT3) were characterized by elemental analysis, FT-IR, UV-Vis, photoluminescence, (1)H and (13)C NMR spectroscopy, and electrochemical techniques by elemental analysis, FT-IR, UV-Vis, photoluminescence, (1)H and (13)C NMR spectroscopy, and electrochemical techniques. The cyclic voltammograms (CVs) of (RBT1), (RBT2), and (RBT3) display reversible one-electron oxidation processes at E 1/2 = 1.13 V, 0.71 V, and 0.99 V, respectively (versus Ag/AgCl). Based on a general linear correlation between increase in the length of π-conjugation bond and the molar extinction coefficients, the Ru(II) bisterpyridyl complexes show characteristic broad and intense metal-to-ligand charge transfer (MLCT) band absorption transitions between 480-600 nm, ε = 9.45 × 10(3) M(-1) cm(-1), and appreciable photoluminescence spanning the visible region.

SUBMITTER: Adeloye AO

PROVIDER: S-EPMC4032701 | biostudies-other | 2014

REPOSITORIES: biostudies-other

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Project description:The series of complexes [XRu(CO)(L-L)(L')2][PF6] (X = H, TFA, Cl; L-L = 2,2'-bipyridyl, 1,10-phenanthroline, 5-amino-1,10-phenanthroline and 4,4'-dicarboxylic-2,2'-bipyridyl; L'2 = 2PPh3, Ph2 PC2H4PPh2, Ph2PCH═CHPPh2) have been synthesized from the starting complex K[Ru(CO)3(TFA)3] (TFA = CF3CO2) by first reacting with the phosphine ligand, followed by reaction with the L-L and anion exchange with NaPF6. In the case of L-L = phenanthroline and L'2 = 2PPh3, the neutral complex Ru(Ph3P)(CO)(1,10-phenanthroline)( TFA)2 is also obtained and its solid state structure is reported. Solid state structures are also reported for the cationic complexes where L-L = phenanthroline, L2 = 2PPh3 and X = Cl and for L-L = 2,2'-bipyridyl, L2 = 2PPh3 and X = H. All the complexes were characterized in solution by a combination of 1H and 31P NMR, IR, mass spectrometry and elemental analyses. The purpose of the project was to synthesize a series of complexes that exhibit a range of excited-state lifetimes and that have large Stokes shifts, high quantum yields and high intrinsic polarizations associated with their metal-to-ligand charge-transfer (MLCT) emissions. To a large degree these goals have been realized in that excited-state lifetimes in the range of 100 ns to over 1 μs are observed. The lifetimes are sensitive to both solvent and the presence of oxygen. The measured quantum yields and intrinsic anisotropies are higher than for previously reported Ru(II) complexes. Interestingly, the neutral complex with one phosphine ligand shows no MLCT emission. Under the conditions of synthesis some of the initially formed complexes with X = TFA are converted to the corresponding hydrides or in the presence of chlorinated solvents to the corresponding chlorides, testifying to the lability of the TFA Ligand. The compounds show multiple reduction potentials which are chemically and electrochemically reversible in a few cases as examined by cyclic voltammetry. The relationships between the observed photophysical properties of the complexes and the nature of the ligands on the Ru(II) is discussed.

Project description:Recent and potential applications of electrochromic materials include smart windows, optoelectronic devices, and energy conversion. In this study, we have incorporated bis(terpyridine) iron (II) complexes into vertically-oriented silica thin films deposited on indium-tin oxide (ITO) and their electrochromic behavior has been investigated. If 2,2':6',2″-terpyridine is commonly used as a ligand for forming metallo-supramolecular assemblies, with the objective to get metal-terpyridine complexes with multiple stable redox states, their simple and reliable arrangement into linear structures enabling effective electronic communication is however more challenging. We propose to overcome this difficulty by generating such complexes within vertical nanochannels on electrode. Terpyridine ligands were firstly immobilized by combining a click chemistry azide/alkyne approach with an electrochemically-assisted self-assembly (EASA) method used to grow an oriented mesoporous silica membrane bearing azide groups which were further derivatized with 4'-ethynyl-terpyridine ligands. The resulting terpyridine-functionalized films were consecutively dipped in an aqueous solution of Fe(BF4)2 and then in a solution of terpyridine in acetonitrile to form the bis(terpyridine) iron (II) complexes in situ. The electrochromic properties of the films functionalized at various levels were examined by monitoring the changes in their UV/Vis spectra upon electrochemical oxidation at controlled potential of +1.2 V vs. Ag/AgCl. Due to facile charge delocalization during the Fe2+ to Fe3+ redox process, the bis(terpyridine) iron (II) functionalized silica films exhibited electrochromic properties by changing from violet to non-colored using TBABF4 in acetonitrile as an electrolyte. The bis(terpyridine) iron(II) film experienced reversible electrochromic switching by applying +0.5 V in a reverse reduction electrochemical process. The Fe(tpy)2-functionalized silica thin films displayed a good contrast ratio (ΔT%) of 47% and relatively high coloration efficiency (CE) of about 245 cm2/C with a response time of coloring and bleaching of a few seconds (< 4 s).

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Synthesis and photophysical and electrochemical properties of functionalized mono-, bis-, and trisanthracenyl bridged Ru(II) bis(2,2':6',2"-terpyridine) charge transfer complexes.

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