18511-69-8Relevant articles and documents
Ruthenium bipyridyl compounds with two terminal alkynyl ligands
Adams, Christopher J.,Bowen, Lucy E.,Humphrey, Mark G.,Morrall, Joseph P. L.,Samoc, Marek,Yellowlees, Lesley J.
, p. 4130 - 4138 (2004)
Compounds of the form Ru(X2bipy)(PPh3) 2(-C≡CC6H4NO2-p)2 (X2 bipy = 4,4′-X2-2,2′-bipyridine, X = Me 3a, Br 3b, I 3c) have been synthesised from the mono-alkynyl precursors Ru(X 2bipy)(PPh3)2(-C≡CC6H 4NO2-p)Cl (X = Me 2a, Br 2b, I 2c); the former are the first ruthenium bis-alkynyl compounds that also contain a bipyridyl ligand. Spectroelectrochemical investigation of 3a shows that the metal is readily oxidised to form the ruthenium(III) compound 3a+, and will also undergo a single-electron reduction at each nitro group to form 3a2-. ESR and UV/visible spectra of these redox congeners are presented. We also report the synthesis of [Ru(Me2bipy)(PPh3) 2-(-C≡CBu1)(N≡N)][PF6] 4 during the attempted synthesis of Ru(Me2bipy)(PPh3) 2(-C≡CBu1)2, and report its X-ray crystal structure and IR spectrum. X-Ray crystal structures of 3b and 3c (as two different solvates) are presented, and the nature of the inlermolecular interactions seen therein is discussed. Z-Scan measurements on Ru(Me 2bipy)(PPh3)2-(-C≡CR)Cl (R = C 6H4NO2-p 2a, But, Ph, C 6H4Me) are also reported, and show that Ru(Me 2bipy)(PPh3)2(-C≡CR)-Cl (R = C 6H4NO2-p 2a, Ph) exhibit moderate third-order non-linearities.
Electrochemistry and spectroscopy of substituted [Ru(phen)3]2+ and [Ru(bpy)3]2+ complexes
van der Westhuizen, Deidré,von Eschwege, Karel G.,Conradie, Jeanet
, (2019)
The metal-to-ligand charge transfer property of nitrogen-based ruthenium complexes earns it a central place in dye-sensitized solar cell and photo-catalytic H2O and CO2 reduction research and applications. Electronic and spectral tuning are conveniently done by altering substituents and ligands. Cyclic voltammograms and UV–visible spectra of a synthesized series of electronically altered phenanthroline and bipyridyl ruthenium complexes (ΔE°' > 1.4 V for RuII-III) were obtained and, amongst others, correlated with DFT computed HOMO energies and ionization potentials. A good linear relationship with R2 = 0.97 were found for the combined bipyridyl and phenanthrolinato ruthenium series, thereby providing a convenient computational tool for the theoretical prediction of associated redox potentials. TDDFT closely simulates spectral properties of these complexes, where λmax varies from 420 to 520 nm. The former wavelength is representative of the dione-phenanthroline and the latter of the dinitro-bipyridyl ruthenium complex.
New bipyridyl ligands bearing azo- and imino-linked chromophores. Synthesis and nonlinear optical studies of related dipolar zinc complexes?
Hilton, Adam,Renouard, Thierry,Maury, Olivier,Le Bozec, Hubert,Ledoux, Isabelle,Zyss, Joseph
, p. 2521 - 2522 (1999)
The synthesis and optical properties of 4,4'-bis(dialkylaminophenylazo)- 2,2'-bipyridine and 4,4'-bis(dialkylaminophenylimino)-2,2'-bipyridine ligands are described; the corresponding dipolar bipyridyl zinc dichloride complexes have been prepared and thei
Long-Lived, Emissive Excited States in Direct and Amide-Linked Thienyl-Substituted RuII Complexes
Majewski, Marek B.,Smith, Jeremy G.,Wolf, Michael O.,Patrick, Brian O.
, p. 1470 - 1479 (2016)
The excited state behavior of a new series of homoleptic and heteroleptic RuII complexes bearing thienyl groups appended to a 2,2′-bipyridine chelating ligand via direct, secondary and tertiary amide linkages is examined. The results of nanosecond transient absorption spectroscopy, emission lifetime measurements and bimolecular quenching experiments are correlated to determine that although the amide linkage does not act as a conjugated bridge to the peripheral substituents, it does not preclude possible electron transfer processes. Complexes bearing directly bound thienyl and bithienyl substituents exhibit long excited state and emission lifetimes (τem = 2 and 15 μs), with high emission quantum yields in solution (Φ = 0.35) and slow rates of non-radiative decay.
Ruthenium(II) photosensitizers with electron-rich diarylamino-functionalized 2,2′-bipyridines and their application in dye-sensitized solar cells
Wang, Qiwei,Wu, Wenjun,Ho, Cheuk-Lam,Xue, Liqin,Lin, Zhenyang,Li, Hua,Lo, Yih Hsing,Wong, Wai-Yeung
, p. 5322 - 5330 (2014)
New ruthenium(II) photosensitizers [Ru(dcbpy)(L)(NCS)2] (dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine; L = 4,4′-bis{di[4-(N,N′-dimethylamino)phenyl]amino}-2,2′-bipyridine (1), 4,4′-bis[di(4-methoxyphenyl)amino]-2,2′-bipyridine (2), and 4,4′-bis[di(4-tolyl)amino]-2,2′-bipyridine (3)) were prepared and characterized and their application in dye-sensitized solar cells is presented. The optical absorption of these photosensitizers gives a peak at around 540 nm, which is very similar to that of the standard N719. The maximum incident photon-to-current conversion efficiency (IPCE) of 80.6% was obtained for 3, which corresponded to a power conversion efficiency (η) of 5.68% under standard air mass (AM) 1.5 sunlight (versus N719 at 6.76%). Molecular cosensitization of 3 with an organic dye, QS-DPP-I, yielded higher η values up to 6% relative to the cells based on individual photosensitizers, and the corresponding IPCE can reach 93.6% at 549 nm. A preliminary stability test of the devices was also conducted.
Improved synthesis of 4,4′-diamino-2,2′-bipyridine from 4,4′-dinitro-2,2′-bipyridine-N,N′-dioxide
Kavanagh, Paul,Leech, Dónal
, p. 121 - 123 (2004)
A superior synthetic route to 4,4′-diamino-2,2′-bipyridine has been developed. This procedure compares favorably with existing methods, producing 4 times the yield previously reported. In addition, mild reaction conditions are utilized, allowing a considerably more efficient production, and subsequent purification, of the diamino complex.
Hydroxyl and amino functionalized cyclometalated Ir(III) complexes: Synthesis, characterization and cytotoxicity studies
Wu, Zhaozhen,Mu, Juanjuan,Wang, Qiong,Chen, Xing,Jensen, Lasse,Yi, Changqing,Li, Mei-Jin
, p. 175 - 182 (2015)
A series of Ir(III) complexes (?N)2Ir(N N) (N N are 4,4′-dihydroxy-2,2′-bipyridine and 4,4′-diamino-2,2′-bipyridine, and ?N are phenylpyridine, benzo[h]quinolone, and 2-phenylquinoline) were synthesized and characterized. Two of the complexes were structurally characterized via X-ray crystallography. The photophysical and photochemical properties of these complexes were studied. Preliminary studies of their applications on pH sensing, and cell imaging were also performed.
A novel cyclometalated Ir(iii) complex based luminescence intensity and lifetime sensor for Cu2+
Shen, Wei,Qi, Zhengjian,Yan, Liqiang,Tian, Wenwen,Cui, Xia,Yao, Hongtao,Sun, Yueming
, p. 16482 - 16488 (2016)
We report the synthesis and characterization of two luminescent cyclometalated Ir(iii) complexes [Ir(dfppy)2(bpy-DPA)]PF6 (Ir-1) and [Ir(dfppy)2(bpy-BiDPA)]PF6 (Ir-2), where dfppy, bpy-DPA and bpy-BiDPA represent 2-(2,4-difluorophenyl)pyridine, N-([2,2′-bipyridine]-4-yl)-2-(bis(pyridin-2-ylmethyl)amino)acetamide and N,N′-([2,2′-bipyridine]-4,4′-diyl)bis(2-(bis(pyridin-2-ylmethyl)amino)acetamide), respectively. Their photophysical properties and sensing properties towards various metal ions were investigated at room temperature. The two complexes both possessed good photophysical properties, and Ir-2 had quite a high quantum yield (93.83%) and a long lifetime (101.17 μs), which is impressive among Ir(iii) complexes. Ir-2 exhibited both high selectivity and sensitivity towards Cu2+ over other metal ions. The Job curve and mass spectra suggested the formation of a 1: 2 bonding mode between Ir-2 and Cu2+. The photoluminescence (PL) intensity quenching curve indicated that Ir-2 could enable rapid and reversible detection of Cu2+ with a low detection limit of 0.85 ppb (13 nM). Furthermore, a linear relationship could be observed between the PL lifetime value of Ir-2 and the concentration of Cu2+ ions in the range of 0-8 μM. These results suggested that Ir-2 might have use as not only a promising photoluminescence intensity sensor, but also a promising lifetime sensor for Cu2+ in aqueous solution.
Electronic effects on reactivity and anticancer activity by half-sandwich N,N-chelated iridium(iii) complexes
Guo, Lihua,Zhang, Hairong,Tian, Meng,Tian, Zhenzhen,Xu, Yanjian,Yang, Yuliang,Peng, Hongwei,Liu, Peng,Liu, Zhe
, p. 16183 - 16192 (2018/10/04)
The synthesis and characterization of a series of organometallic half-sandwich N,N-chelated iridium(iii) complexes bearing a range of electron-donating and withdrawing substituents were described. The X-ray crystal structures of complexes 1, 3 and 5 have been determined. This work demonstrated how the aqueous chemistry, catalytic activity in converting coenzyme NADH to NAD+ and anticancer activity can be controlled and fine-tuned by the modification of the ligand electronic perturbations. In general, the introduction of an electron-withdrawing group (-Cl and-NO2) on the bipyridine ring resulted in increased anticancer activity, whereas an electron-donating group (-NH2,-OH and-OCH3) decreased the anticancer activity. Complex 6 bearing a strongly electron-withdrawing NO2 group displayed the highest anticancer activity (7.3 ± 1.2 μM), ca. three times as active as cisplatin in the A549 cell line. Notably, selective cytotoxicity for cancer cells over normal cells was observed for complexes 1 and 6. DNA binding does not seem to be the primary mechanism for cancer fighting. However, the aqueous chemistry, cell apoptosis and cell cycle, which show similar dependence on the ligand electronic perturbations as the anticancer activity, appear to together contribute to the anticancer potency of theses complexes. This work may provide an alternative strategy to enhance anticancer activity for these N,N-chelated organometallic half-sandwich iridium(iii) complexes.
In order to BipySi for preparation of the prismatic body cage oligomeric silsesquioxane and its rare earth luminescent material
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, (2017/08/25)
The invention relates to a cage type oligomeric silsesquioxane prepared by taking BipySi as supplement bodies and a rare earth luminescent material prepared from cage type oligomeric silsesquioxane. By taking 1,3,5,7,9,11,14-heptaisobutyl tricyclic[7,3.3.15,11] heptatrisiloxane-intra-3,7,14-triol as a matrix, alpha-thenoyl trifluoroacetone silanized derivative, a dipyridine silanized derivative and a terpyridyl silanized derivative as supplement bodies, the supplement bodies react with the matrix in form of supplements to form integrated novel cage type oligomeric silsesquioxane. The cage type oligomeric silsesquioxane is combined with rare earth elements to form a POSS/rare earth ion luminescent material. The obtained rare earth ion luminescent material/POSS is rich in luminescent color, high in color purity, long in fluorescent lifetime (0.5-1.5ms), high in quantum efficiency (20) and strong in thermal stability (350 DEG C) and light stability, is a valuable optical material and can be applied to the field of display and development, light source, X-ray intensifying screen and the like.
