Polymeric ruthenium bipyridine complexes: New potential materials for polymer solar cells

Methyl methacrylate‐containing bipyridine monomers were synthesized with a hydoxy‐functionalized bipyridine. The 4′‐methyl group of the 2,2′‐bipyridine was used to introduce hydoxy‐functionalized alkyl spacers of two different lengths. Two, different synthetic routes were applied for the preparation of the hydoxy‐functionalized bipyridine via a bromo‐(C₇ spacer) or a silylated‐(C₃ spacer) intermediate. A copolymer of poly(methyl methacrylate) with bipyridine units in the side chains was prepared by free‐radical copolymerization and characterized with ¹H NMR, ultraviolet–visible, and IR spectroscopy as well as gel permeation chromatography. The bipyridine units of the copolymer were reacted with ruthenium bipyridine precursors. The resulting graft copolymers displayed promising photophysical and electrochemical properties, opening interesting perspectives for applications in the field of solar‐cell devices. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 374–385, 2004     

Mixed iridium(III) and ruthenium(II) polypyridyl complexes containing poly(ε‐caprolactone)‐bipyridine macroligands

A hydroxy‐functionalized bipyridine ligand was polymerized with ε‐caprolactone utilizing the controlled ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate. The resulting poly(ε‐caprolactone)‐containing bipyridine was characterized by ¹H NMR and IR spectroscopy, and gel permeation chromatography, as well as matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, revealing the successful incorporation of the bipyridine ligand into the polymer chain. Coordination to iridium(III) and ruthenium(II) precursor complexes yielded two macroligand complexes, which were characterized by NMR, gel permeation chromatography, matrix‐assisted laser desorption/ionization time‐of‐flight MS, cyclic voltammetry, and differential scanning calorimetry. In addition, both photophysical and electrochemical properties of the metal‐containing polymers proved the formation of a trisruthenium(II) and a trisiridium(III) polypyridyl species, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4153–4160, 2004     

Stereocontrol in the free‐radical polymerization of methacrylates with fluoroalcohols

The free‐radical polymerization of methyl methacrylate (MMA), ethyl methacrylate (EMA), isopropyl methacrylate (IPMA), and tert‐butyl methacrylate (t‐BuMA) was carried out under various conditions to achieve stereoregulation. In the MMA polymerization, syndiotactic specificity was enhanced by the use of fluoroalcohols, including (CF₃)₃COH as a solvent or an additive. The polymerization of MMA in (CF₃)₃COH at −98 °C achieved the highest syndiotacticity (rr = 93%) for the radical polymerization of methacrylates. Similar effects of fluoroalcohols enhancing syndiotactic specificity were also observed in the polymerization of EMA, whereas the effect was negligible in the IPMA polymerization. In contrast to the polymerizations of MMA and EMA, syndiotactic specificity was decreased by the use of (CF₃)₃COH in the t‐BuMA polymerization. The stereoeffects of fluoroalcohols seemed to be due to the hydrogen‐bonding interaction of the alcohols with monomers and growing species. The interaction was confirmed by NMR measurements. In addition, in the bulk polymerization of MMA at −78 °C, syndiotactic specificity and polymer yield increased even in the presence of a small amount {[(CF₃)₃COH]/[MMA]_o < 1} of (CF₃)₃COH. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4693–4703, 2000     

Luminescence characteristics and X‐ray crystal structure of [Cd(bipy)3][PF6]2 (bipy = 2,2′‐bipyridine)

The photoluminescence characteristics of the [Cd(bipy)₃][PF₆]₂ complex are reported. A moderately large quantum yield (φ) of 1.07 × 10^?2 is exhibited in acetonitrile solution at 298 K. Crystallography shows the dication to have a distorted octahedral geometry and the crystal structure to be stabilized by C? H···π and C? H···F interactions. Copyright © 2005 John Wiley & Sons, Ltd.     

Electrochemiluminescence of Tris(2,2′‐bipyridine)ruthenium with Various Co‐reactants under Ultrasound Irradiation

Electrochemiluminescence (ECL) of tris(2,2′‐bipyridine)ruthenium, Ru(bpy)₃²⁺ in the presence of various co‐reactants, such as tripropylamine (TPA), oxalate ion (C₂O₄^2?), ascorbic acid (H₂A) and dehydroascorbic acid (DHA), were investigated under ultrasound irradiation. In sono‐ECL experiments, an indium‐thin‐oxide (ITO) was used as working electrode, and a titanium tipped sonic horn probe (diameter 2 mm) which operated at a frequency of 20 kHz was set in the front of the ITO electrode. Under the ultrasound irradiation, ECL signals were found to be significantly enhanced when TPA and C₂O₄^2? were used as co‐reactants, only slightly enhanced in Ru(bpy)₃²⁺/DHA system, but total quenched in Ru(bpy)₃²⁺/H₂A system. The difference of Ru(bpy)₃²⁺ ECL behaviors for various co‐reactant could to be due to the different kinetics of catalytic reactions associated in ECL schemes. ECL quenching effect observed in Ru(bpy)₃²⁺/H₂A system was suggested to be due to electron transfer (ET) route between the excited state *Ru(bpy)₃²⁺ and ascorbate anion HA^? diffused from the bulk solution, where the diffusional HA^? species served as electron donor. The effect becomes more pronounced upon sonication because the effective collision frequency between *Ru(bpy)₃²⁺ and HA^? would be significantly increased by the enhanced mass transport effect of ultrasound.     

Metal complexes with polymeric ligands: Chelation and metalloinitiation approaches to metal tris(bipyridine)‐containing materials

Synthetic approaches to metal complexes with polymeric ligands are described. The development of efficient methods for preparing simple bipyridine (bpy) derivatives and their corresponding metal complexes has facilitated their use as initiators and coupling agents in polymer syntheses. Ligand reagents were utilized as initiators in controlled polymerization reactions to form poly(2‐R‐2‐oxazolines) (R = methyl, ethyl, phenyl, undecyl), polystyrenes, poly(methyl methacrylates) (PMMA)s, poly(ϵ‐caprolactone)s, and poly(lactic acid)s with bipyridine chelates at the end or centers of the chains. Poly(ethylene glycol) macroligands were formed by a chain‐coupling method. Detailed studies of reaction kinetics were performed to determine the scope and limitations of each reaction type with different catalysts and reaction conditions. These results are illustrated for bpyPMMA_n (n = 1 or 2), which was prepared by atom transfer radical polymerization with a CuBr/1,4,4,7,7,10‐hexamethyltriethylenetetraamine catalyst system. Results of the kinetics investigations performed with other ligands and metalloinitiators are summarized. Macroligands thus prepared were coordinated to a labile metal ion, Fe(II), with standard protocols. Ultraviolet–visible spectral data for selected Fe‐centered polymers are provided that confirm the production of the targeted polymeric iron complex products. An inert metal, Ru(II), was used as a template for generating architectural diversity; polymeric complexes with one to six chains emanating from the central core, as well as different heteroarm star products, were prepared. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4704–4716, 2000     

A Bifunctional Electrocatalyst Containing Tris(2,2′‐bipyridine) Ruthenium(II) and 12‐Molybdophosphate Bulk‐Modified Carbon Paste Electrode

The electroactive composite containing tris(2,2′‐bipyridine) ruthenium(II) and 12‐molybdophosphate (RuPMo₁₂) was synthesized and first used as a bifunctional electrocatalyst to fabricate a chemically bulk‐modified carbon paste electrode (RuPMo₁₂‐CPE) by direct mixing. The electrochemical behavior of the RuPMo₁₂‐CPE was studied by cyclic voltammetry. The RuPMo₁₂‐CPE presents good electrocatalytic activity not only toward the reduction of hydrogen peroxide and bromate, which is attributed to the function of molybdophosphate, but also toward the oxidation of arsenite, which is primarily attributed to the function of tris(2,2′‐bipyridine) ruthenium(II). The remarkable advantage of the RuPMo₁₂‐CPE is its good stability owing to the insolubility of RuPMo₁₂ and reproducibility of surface renewal.     

Synthesis and characterization of well‐defined ABC‐type triblock copolymers via atom transfer radical polymerization and stable free‐radical polymerization

An asymmetric difunctional initiator 2‐phenyl‐2‐[(2,2,6,6 tetramethylpiperidino)oxy] ethyl 2‐bromo propanoate ( 1 ) was used for the synthesis of ABC‐type methyl methacrylate (MMA)‐tert‐butylacrylate (tBA)‐styrene (St) triblock copolymers via a combination of atom transfer radical polymerization (ATRP) and stable free‐radical polymerization (SFRP). The ATRP‐ATRP‐SFRP or SFRP‐ATRP‐ATRP route led to ABC‐type triblock copolymers with controlled molecular weight and moderate polydispersity (M_w/M_n < 1.35). The block copolymers were characterized by gel permeation chromatography and ¹H NMR. The retaining chain‐end functionality and the applying halide exchange afforded high blocking efficiency as well as maintained control over entire routes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2025–2032, 2002     

Luminescent polymeric ruthenium complexes with polystyrene‐b‐poly(methyl methacrylate) macroligands: The sequential activation of initiator sites for blocks generated by parallel polymerization mechanisms

The synthesis of polystyrene‐b‐poly(methyl methacrylate) diblock copolymers with a luminescent ruthenium(II) tris(bipyridine) [Ru(bpy)₃] complex at the block junction is described. The macroligand precursor, polystyrene bipyridine‐poly(methyl methacrylate) [bpy(PS–H)(PMMA)], was synthesized via the atom transfer radical polymerization of styrene and methyl methacrylate from two independent, sequentially activated initiating sites. Both polymerization steps resulted in the growth of blocks with sizes consistent with monomer loading and narrow molecular weight distributions (i.e., polydispersity index < 1.3). Subsequent reactions with ruthenium(II) bis(bipyridine) dichloride [Ru(bpy)₂Cl₂] in the presence of Ag⁺ generated the ruthenium tris(bipyridine)‐centered diblock, which is of interest for the imaging of block copolymer microstructures and for incorporation into new photonic materials. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4250–4255, 2002     

Quality control of PET radiopharmaceuticals by high‐performance liquid chromatography with tris(2,2′‐bipyridyl)ruthenium(II) electrogenerated chemiluminescence detection

A highly sensitive reversed‐phase liquid chromatographic (HPLC) method was investigated to analyze a range of positron emission tomography (PET) radiopharmaceuticals using electrogenerated chemiluminescence (ECL) detection. ECL is based on the reaction of PET molecules with tris(2,2′‐bipyridyl)ruthenium(III) [Ru(bpy)₃³⁺], which is generated through the on‐line electro‐oxidation of Ru(bpy)₃²⁺. In 21 different radiopharmaceuticals studied, 18 compounds could be detected with detection limits (signal‐to‐noise ratio = 3) of 0.12–72 ng/mL per 20 μL injection. Sufficient reproducibility and linearity were obtained for the quantitative determination of PET molecules in pharmaceutical fluid. This method could be successfully applied to quality control tests of PET radiopharmaceuticals with ultra‐high specific radioactivity. Copyright © 2009 John Wiley & Sons, Ltd.     

1H NMR assignment corrections and 1H, 13C, 15N NMR coordination shifts structural correlations in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline

¹H, ¹³C and ¹⁵N NMR studies of iron(II), ruthenium(II) and osmium(II) tris‐chelated cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline of the general formula [M(LL)₃]²⁺ (M = Fe, Ru, Os; LL = bpy, phen) were performed. Inconsistent literature ¹H signal assignments were corrected. Significant shielding of nitrogen‐adjacent protons [H(6) in bpy, H(2) in phen] and metal‐bonded nitrogens was observed, being enhanced in the series Ru(II) → Os(II) → Fe(II) for ¹H, Fe(II) → Ru(II) → Os(II) for ¹⁵N and bpy → phen for both nuclei. The carbons are deshielded, the effect increasing in the order Ru(II) → Os(II) → Fe(II). Copyright © 2010 John Wiley & Sons, Ltd.     

Side‐chain terpyridine polymers through atom transfer radical polymerization and their ruthenium complexes

Polymers containing side‐chain terpyridine ligands of well‐defined architectures and controllable molecular weights and molecular weight distributions are reported. These polymers were synthesized by the atom transfer radical polymerization (ATRP) of a newly synthesized terpyridine monomer with three functional initiators. The obtained polymers were characterized with ¹H NMR and gel permeation chromatography techniques. The efficiency of the ATRP technique and the overall control of the molecular characteristics of the polymers were demonstrated by a kinetic study of the polymerization reaction. Subsequently, the ruthenium(III)/ruthenium(II) complexation chemistry was employed for the attachment of bis(dodecyloxy)‐functionalized terpyridine moieties onto each side 2,2′:6′,2″‐terpyridine unit of the main polymeric backbone. Thus, the grafting approach was successfully combined with the metal–ligand coordination chemistry for the preparation of highly soluble polymeric complexes. The resulting complexes were fully characterized by means of ¹H NMR, gel permeation chromatography, and ultraviolet–visible spectroscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4838–4848, 2005     

Tris(2,2′‐bipyridyl)ruthenium(II) Electrogenerated Chemiluminescence Sensor Based on Platinized Carbon Nanotube–Zirconia–Nafion Composite Films

Mesoporous films of platinized carbon nanotube–zirconia–Nafion composite have been used for the immobilization of tris(2,2′‐bipyridyl)ruthenium (II) (Ru(bpy)₃²⁺) on an electrode surface to yield a solid‐state electrogenerated chemiluminescence (ECL) sensor. The composite films of Pt–CNT–zirconia–Nafion exhibit much larger pore diameter (3.55 nm) than that of Nafion (2.82 nm) and thus leading to much larger ECL response for tripropylamine (TPA) because of the fast diffusion of the analyte within the films. Due to the conducting and electrocatalytic features of CNTs and Pt nanoparticles, their incorporation into the zirconia–Nafion composite films resulted in the decreased electron transfer resistance within the films. The present ECL sensor based on the Pt–CNT–zirconia–Nafion gave a linear response (R²=0.999) for TPA concentration from 3.0 nM to 1.0 mM with a remarkable detection limit (S/N=3) of 1.0 nM, which is much lower compared to those obtained with the ECL sensors based on other types of sol‐gel ceramic–Nafion composite films such as silica–Nafion and titania–Nafion.     

Emulsion atom transfer radical block copolymerization of 2‐ethylhexyl methacrylate and methyl methacrylate

The emulsion atom transfer radical block copolymerization of 2‐ethylhexyl methacrylate (EHMA) and methyl methacrylate (MMA) was carried out with the bifunctional initiator 1,4‐butylene glycol di(2‐bromoisobutyrate). The system was mediated by copper bromide/4,4′‐dinonyl‐2,2′‐bipyridyl and stabilized by polyoxyethylene sorbitan monooleate. The effects of the initiator concentration and temperature profile on the polymerization kinetics and latex stability were systematically examined. Both EHMA homopolymerization and successive copolymerization with MMA proceeded in a living manner and gave good control over the polymer molecular weights. The polymer molecular weights increased linearly with the monomer conversion with polydispersities lower than 1.2. A low‐temperature prepolymerization step was found to be helpful in stabilizing the latex systems, whereas further polymerization at an elevated temperature ensured high conversion rates. The EHMA polymers were effective as macroinitiators for initiating the block polymerization of MMA. Triblock poly(methyl methacrylate–2‐ethylhexyl methacrylate–methyl methacrylate) samples with various block lengths were synthesized. The MMA and EHMA reactivity ratios determined by a nonlinear least‐square method were ～0.903 and ～0.930, respectively, at 70 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1914–1925, 2006     

Molecular geometry and electronic structure of molecules in free‐radical copolymerization of styrene and methyl methacrylate derived from density functional calculations

The molecular geometry and electronic structure of styrene and methyl methacrylate as well as corresponding radicals formed by the addition of a methyl radical to the β‐carbon of the monomer were determined using the density functional theory at the B3LYP/6‐311+G** level. Results were in good agreement with the theoretical and experimental data available in the literature. Full optimized molecular geometry of methyl methacrylate showed the trans form of the molecule. Monomers transformed into corresponding radicals preserved the main structural parameters of substituents whereas bonds between substituents and adjacent radical carbon atoms shortened. It was found that the correlation of the theoretically calculated electronic parameters for monomers and the corresponding radicals with the Q and e parameters from the Alfrey–Price scheme strongly depends on the level of calculations. Application of the higher level of theory including the correlation effect changes the relationship discussed in the literature between energy (E_Y) of formation of a radical from the monomer, the experimental e parameter, and the Q parameter and monomer/average electronegativity, respectively. The total atomic spin density at the radical carbon atom correlated with the radical parameter P in the Alfrey–Price scheme was computed to be higher for the methoxycarbonyl‐1‐methyl‐ethyl radical when compared with the 1‐phenyl‐propyl radical. These values are in good agreement with the localization energies and the P values determined from the kinetic measurements for macroradicals ending with styrene and methyl methacrylate monomer units. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3761–3769, 2001     

Effect of temperature and solvent on polymer tacticity in the free‐radical polymerization of styrene and methyl methacrylate

The effect of temperature and solvent on polymer tacticity in free‐radical polymerization of styrene and methyl methacrylate was studied by ¹³C and ¹H NMR, respectively. Polystyrene shows a mild syndiotactic tendency (P_m = 0.36 ± 0.02) that is independent of temperature over a wide range (?10 to 120 °C), while poly(methyl methacrylate) shows a stronger syndiotactic tendency (P_m = 0.17 ± 0.01 at 30 °C) that decreases as temperature is increased (P_m = 0.22 ± 0.02 at 80 °C). None of the polymerization solvents studied (bulk, THF, DMF, DMSO, acetonitrile, and acetone) had a significant effect on polymer tacticity in either system. The triad fractions of both polymers showed deviations from the Bernoulli model, implying that the antepenultimate unit affects the propagation reaction. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3351–3358     

Synthesis,characterization, and biological and anticancer studies of mixed ligand complexes with Schiff base and 2,2′‐bipyridine

New mixed ligand complexes of transition metals were synthesized from a Schiff base (L¹) obtained by the condensation reaction of oxamide and furfural as primary ligand and 2,2′‐bipyridine (L²) as secondary ligand. The ligands and their metal complexes were studied using various spectroscopic methods. Also thermal analyses were conducted. The mixed ligand complexes were found to have formulae [M(L¹)(L²)]Cl_m ⋅n H₂O (M = Cr(III) and Fe(III): m  = 3, n  = 0; M = Cu(II) and Cd(II): m  = 2, n  = 1; M = Mn(II), Co(II), Ni(II) and Zn(II): m  = 2, n  = 0). The resultant data revealed that the metal complexes have octahedral structure. Also, the mixed ligand complexes are electrolytic. The biological and anticancer activities of the new compounds were tested against breast cancer (MCF‐7) and colon cancer (HCT‐116) cell lines. The results showed high activity for the synthesized compounds.     

Tris(2,2′‐bipyridine)iron(II) bis(1,1,3,3‐tetracyano‐2‐ethoxypropenide) dihydrate: chiral hydrogen‐bonded frameworks interpenetrate in three dimensions

In the title compound, [Fe(C₁₀H₈N₂)₃](C₉H₅N₄O)₂·2H₂O, the chiral cations lie across twofold rotation axes in the space group C2/c. The anions and the water molecules are linked by two independent O—H...N hydrogen bonds to form C₂²(8) chains, and these chains are linked by the cations via C—H...N and C—H...O hydrogen bonds to form two interpenetrating three‐dimensional frameworks, each of which contains only one enantiomeric form of the chiral cation.     

Nitroxide‐mediated radical copolymerization of methyl methacrylate controlled with a minimal amount of 9‐(4‐vinylbenzyl)‐9H‐carbazole

The controlled nitroxide‐mediated homopolymerization of 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) and the copolymerization of methyl methacrylate (MMA) with varying amounts of VBK were accomplished by using 10 mol % {tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino} nitroxide relative to 2‐({tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino}oxy)‐2‐methylpropionic acid (BlocBuilder?) in dimethylformamide at temperatures from 80 to 125 °C. As little as 1 mol % of VBK in the feed was required to obtain a controlled copolymerization of an MMA/VBK mixture, resulting in a linear increase in molecular weight versus conversion with a narrow molecular weight distribution (M_w /M_n ≈ 1.3). Preferential incorporation of VBK into the copolymer was indicated by the MMA/VBK reactivity ratios determined: r_VBK = 2.7 ± 1.5 and r_MMA = 0.24 ± 0.14. The copolymers were found significantly “living” by performing subsequent chain extensions with a fresh batch of VBK and by ³¹P NMR spectroscopy analysis. VBK was found to be an effective controlling comonomer for NMP of MMA, and such low levels of VBK comonomer ensured transparency in the final copolymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Homogeneous radical polymerization of 2‐hydroxyethyl methacrylate mediated by cyclometalated cationic Ruthenium(II) complexes with PF6− and Cl− in protic media

Cationic coordinatively saturated complexes of ruthenium(II), [Ru(o‐C₆H₄‐2‐py)(phen)(MeCN)₂]⁺, bearing different counterions of PF₆^? and Cl^? have been used in the radical polymerization of 2‐hydroxyethyl methacrylate in protic media and acetone under homogeneous conditions. Exchange of PF₆^? by Cl^? increases the solubility of the complex in water. Both complexes led to the fast polymerization under mild conditions, but control was achieved only in methanol and acetone and was better for the complex with Cl^?. The polymerization accelerated in aqueous media and proceeded to a high conversion even with a monomer/catalyst = 2000/1, but without control. Polymerization mediated by complex bearing Cl^? was slower in protic solvents but faster in acetone and always resulted in lower molecular weight polymers. Thus, the nature of the anion strongly affected the catalytic activity of the complexes and may serve as way of fine‐tuning the catalytic properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011