148332-31-4Relevant articles and documents
Ruthenium Complex-Incorporated Two-Dimensional Metal-Organic Frameworks for Cocatalyst-Free Photocatalytic Proton Reduction from Water
Chen, Hong,Chen, Shani,Duan, Lele,Huo, Debiao,Ji, Yongfei,Lin, Feifei,Ni, Yueran,Tong, Lianpeng,Wang, Ranhao,Zhou, Aiju
, p. 2379 - 2386 (2020)
Ultrathin two-dimensional (2D) nanosheets with efficient light-driven proton reduction activity were obtained through the exfoliation of novel metal-organic frameworks (MOF), which were synthesized by using a bis(4′-carboxy-2,2′:6′,2″-terpyridine) ruthenium complex as a linker and 3d transition-metal (Mn, Co, Ni, and Zn) anions as nodes. The nanosheet of the Ni2+ node exhibits a photocatalytic hydrogen evolution rate of 923 ± 40 μmol g-1 h-1 at pH = 4.0, without the presence of any cocatalyst or cosensitizer. A combined experimental and theoretical study suggests a reductive quenched pathway for the photocatalytic hydrogen evolution by the nanosheet. The transition-metal nodes at the edge of the nanosheets are proposed as the active sites. Density functional theory (DFT) calculations attributed the different catalytic activities of the nanosheets to the discrepancy of H adsorption free energy at various transition-metal nodes.
Terpyridine- and 2,6-dipyrazinylpyridine-coordinated ruthenium(II) complexes: Synthesis, characterization and application in TiO2-based dye-sensitized solar cells
Vougioukalakis, Georgios C.,Stergiopoulos, Thomas,Kantonis, Georgios,Kontos, Athanassios G.,Papadopoulos, Kyriakos,Stublla, Arta,Potvin, Pierre G.,Falaras, Polycarpos
, p. 22 - 32 (2010)
Two new ruthenium(II) complexes bearing terpyridine- or 2,6-dipyrazinylpyridine ligands have been prepared and characterized by one- and two-dimensional NMR techniques, ESI mass spectrometry, as well as by UV-vis, emission, FTIR, Raman, and cyclic voltammetry studies. The structure of the terpyridine-coordinated complex resembles that of black dye (tris(thiocyanato) (2,2′:6′,2″-terpyridyl-4,4′,4″-tricarboxylato) ruthenium(II) tris(tetra butylammonium) salt), while the spectral data of the 2,6-dipyrazinylpyridine-coordinated complex are consistent with an unanticipated, unsymmetrical binuclear structure. The ruthenium(II)/(III) oxidation potential of the terpyridine-coordinated dye was measured at +0.87 V (vs. Ag/AgCl), about 200 mV higher than the oxidation potential of black dye. According to a series of desorption experiments, both new dyes were found to adsorb on TiO2 to a greater extent than black dye. The photo-electrochemical properties of both dyes were investigated and compared to that of black dye; while the 2,6-dipyrazinylpyridine-coordinated complex was found to be a very poor sensitizer, the cells obtained from the terpyridine-coordinated dye show power-conversion efficiencies which are more than half of that attained by black dye. Finally, preliminary electron dynamics studies of the cells constructed with the terpyridine dye were carried out and the results are compared to that of black dye cells.
Understanding the Excited State Behavior of Cyclometalated Bis(tridentate)ruthenium(II) Complexes: A Combined Experimental and Theoretical Study
Kreitner, Christoph,Erdmann, Elisa,Seidel, Wolfram W.,Heinze, Katja
, p. 11088 - 11104 (2015)
The synthesis and characterization of the donor-acceptor substituted cyclometalated ruthenium(II) polypyridine complex isomers [Ru(dpb-NHCOMe)(tpy-COOEt)](PF6) 1(PF6) and [Ru(dpb-COOEt)(tpy-NHCOMe)](PF6) 2(PF6)
Synthesis of a new metal chelating amino acid: Terpyridyl-alanine
Schneider, Tobias,Gavrilova, Ivana,Budisa, Nediljko
, p. 906 - 910 (2019)
In past years, terpyridine-containing substances have been found useful in polynucleotide chemistry and enzymatic engineering applications. Therefore, the construction of a noncanonical amino acid with a terpyridine side chain may offer promising features for in vitro and in vivo applications, such as the direct bio-expression of proteins with these substances as building blocks. The first step towards these goals is to establish a synthetic protocol for a terpyridine analog bearing an amino acid moiety. Here, we demonstrate the synthesis of terpyridyl-alanine for the first time in five steps and an overall yield of 50%. A metal complex with Fe(II) ions was prepared by crystallization of a protected terpyridyl-alanine derivative and analyzed by X-ray crystallography. Complex formation in aqueous solution was studied by 1H-NMR, UV/Vis and fluorescence spectroscopy. The comparison of five transition metal ions revealed a metal dependent shift in the UV-absorption and a strong fluorescence in the presence of Zn(II) ions.
Covalent hybrids based on Re(i) tricarbonyl complexes and polypyridine-functionalized polyoxometalate: Synthesis, characterization and electronic properties
Auvray, Thomas,Santoni, Marie-Pierre,Hasenknopf, Bernold,Hanan, Garry S.
, p. 10029 - 10036 (2017/08/10)
A series of [Re(CO)3Br(N^N)] (N^N = substituted 2,2′-bipyridine ligand) complexes based on polypyridine-functionalized Dawson polyoxometalate (1-3) has been synthesized. The new hybrids (4-6) were characterized by various analytical techniques, including absorption, vibrational and luminescence spectroscopies as well as electrochemistry. Both units, the polyoxometalate and the transition metal complex, retain their intrinsic properties. Their combination in the newly prepared hybrids results in improved photosensitization in the high-energy visible region. However, a complete quenching of the emission for the [Re(CO)3Br(N^N)] complexes is observed due to formation of a charge separated state, Re(ii)-POM-, as shown by quenching experiments as well as theoretical modelling via DFT.
Synthesis of unsymmetrically substituted bipyridines by palladium-catalyzed direct C-H arylation of pyridine N -oxides
Duric, Sasa,Tzschucke, C. Christoph
, p. 2310 - 2313 (2011/06/28)
Chemical equations presented. Substituted bipyridines were efficiently prepared by direct coupling between pyridine N-oxides and halopyridines using a palladium catalyst. Pyridine N-oxides with electron-withdrawing substitutents gave the best yields. This method allows the convenient preparation of 2,2′-, 2,3′-, and 2,4′-bipyridines which are useful as functionalized ligands for metal complexes or as building blocks for supramolecular architectures.
Ruthenium(II) complexes of carboxylated terpyridines and dipyrazinylpyridines
Stublla, Arta,Potvin, Pierre G.
scheme or table, p. 3040 - 3050 (2011/01/10)
One-pot preparations of carboxylated 2,2′6′,2Prime;-terpyridine and 2,6-dipy:razin-2-ylpyridine ligands are reported, in free acid and ester forms, as well as their transformations to homoleptic RuII complexes in very good yields. Density functional theory calculations of their geometry-optimized structures enabled their comparison with crystal, structures; although the gross features of the crystal structures were reproduced, they showed much variability and distortion. The spectroscopic and electrochemical properties were analyzed from, the point of view of their geometry-optimized, structures, molecular orbital characteristics and electronic transitions, specifically to assess the effects of carboxylation and of inserting a phenylene spacer between the tridentate portion and the carboxyl group. The dipyrazinylpyridine complexes had HOMO levels stabilized by approximately 1 eV relative to the terpyridine analogues, and showed positive-shifted electrochemical potentials and redshifted electronic absorptions. Phenylene spacers were found to act as electron-donating groups, and the lowest-energy UV/Vis transitions showed intraligand character.
Carboxylate derivatives of oligopyridines
Fallahpour, Reza-Ali
, p. 1138 - 1142 (2007/10/03)
The key compound ethyl 2,6-dibromopyridine-4-carboxylate was prepared in two steps starting from the commercially available citrazinic acid. By using the Stille coupling reaction ethyl 2,6- dibromopyridine-4-carboxylate was converted to 2,2'-bipyridines, 2,2':6',2''-terpyridines and 2,2':6',2'':6'',2''':6''',2''''- quinquepyridines which bear a carboxylate functional group directly attached to the central pyridine ring.
