136276-24-9Relevant academic research and scientific papers
Stimuli-Responsive Luminescent Bis-Tridentate Ru(II) Complexes toward the Design of Functional Materials
Bar, Manoranjan,Deb, Sourav,Paul, Animesh,Baitalik, Sujoy
, p. 12010 - 12024 (2018)
We report here the synthesis, characterization, and photophysics of two bis-tridentate Ru(II) complexes based on a heteroditopic ligand and thoroughly studied their stimuli-responsive behaviors toward the design of functional materials. Both complexes display emission at room temperature having lifetimes in the range of 0.5-70.0 ns, depending on coligand and solvent. Substantial modulations of absorption and emission spectral behaviors of the complexes were done upon interaction with anions, and anion-induced changes in the properties lead to recognition of selected anions in both organic and aqueous media. Photophysical properties of the complexes were also tuned by changing the pH of the medium, and pKa values in both ground and excited states were determined. The presence of free pyridine-imidazole motifs in the complexes leads to substantial modulation of the optical properties and switching of the emission properties upon interaction with selected cations as well as with protons. Fe2+, Co2+, Ni2+, and Cu2+ trigger emission quenching, while Zn2+ induces finite enhancement of the emission intensity in the complexes. In essence, modulation of the optical properties and switching of luminescence properties of the complexes were accomplished by a variety of the external stimuli such as anions, cations, protons, and pH, as well as solvent polarity. Importantly, the optical outputs in response to an appropriate set of stimuli were utilized to mimic the functions of two-input IMPLICATION, NOR, and XNOR logic gates.
Perylene-based, bis(terpyridine)-ru(ii) complexes: synthesis, electrochemical and photovoltaic properties
El-Batal, Hany,Rocha, Juan Manrquez,Mndez, Perla F.,Godnez, Luis A.,Guo, Kai,Li, Xiaopeng,Lu, Xiaocun,Wesdemiotis, Chrys,Moorefield, Charles N.,Newkome, George R.
, p. 502 - 514 (2015)
Perylene-based, terpyridine-Ru(II) complexes are synthesized and their electrochemical and photoelectrochemical properties are studied; their fabrication into dye-sensitized solar cells are described (DSSCs) and their resultant photovoltaic properties are
Synthesis, stability and sensitised lanthanide luminescence of heterobimetallic d/f terpyridine complexes
Moore, Evan G.,Benaglia, Massimo,Bergamini, Giacomo,Ceroni, Paola
, p. 414 - 420 (2015)
The synthesis, solution behavior and photophysical properties of several heteronuclear bimetallic d/f complexes that utilise a RuII bis-terpyridine moiety as the sensitiser for EuIII, NdIII and YbIII luminescenc
Identification of a chemical fingerprint linking the undeclared 2017 release of 106Ru to advanced nuclear fuel reprocessing
Botti, Adrian,Cooke, Michael W.,Steinhauser, Georg,Ungar, Kurt R.,Zok, Dorian
, p. 14703 - 14711 (2020)
The undeclared release and subsequent detection of ruthenium-106 (106Ru) across Europe from late September to early October of 2017 prompted an international effort to ascertain the circumstances of the event. While dispersion modeling, corrobo
Demonstration of intramolecular energy transfer in asymmetric bimetallic ruthenium(II) complexes
Bar, Manoranjan,Maity, Dinesh,Das, Shyamal,Baitalik, Sujoy
, p. 17241 - 17253 (2016)
A new family of bimetallic Ru(ii) complexes derived from an asymmetric bridging ligand (tpy-Hbzim-dipy) consisting of both bipyridine and terpyridine chelating sites covalently connected via phenyl-imidazole spacer were designed in this work to demonstrate intramolecular energy transfer from one component to the other in asymmetric dyads. To fine tune the photo-redox properties, both bidentate and tridentate terminal ligands in the complexes were varied systematically. Both steady state and time-resolved luminescence spectral results indicated photo-induced intramolecular energy transfer from the excited MLCT state of the [(bpy/phen)2RuII(dipy-Hbzim-tpy)] component to the MLCT state of the tpy-containing unit [(dipy-Hbzim-tpy)RuII(tpy-PhCH3/H2pbbzim)] in dyads with rate constant values on the order of 106-107 s-1. Temperature-dependent luminescence studies indicated an enhancement in the luminescence intensity and excited state lifetimes upon decreasing the temperature.
Luminescent bis-tridentate ruthenium(ii) and osmium(ii) complexes based on terpyridyl-imidazole ligand: Synthesis, structural characterization, photophysical, electrochemical, and solvent dependence studies
Bhaumik, Chanchal,Das, Shyamal,Maity, Dinesh,Baitalik, Sujoy
, p. 2427 - 2438 (2012)
Homo- and heteroleptic bis-tridentate ruthenium(ii) and osmium(ii) complexes of compositions [(tpy-PhCH3)Ru(tpy-HImzPh 3)](ClO4)2 (1), [(H2pbbzim)Ru(tpy- HImzPh3)] (ClO4)2 (2) and [M(tpy-HImzPh 3)2](ClO4)2 [M = RuII (3) and OsII (4)], where tpy-PhCH3 = p-methylphenyl terpyridine, H2pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-HImzPh3 = 4′-[4-(4,5-diphenyl-1H-imidazol-2-yl)-phenyl]-[2, 2′:6′,2′′]terpyridine, have been synthesized and characterized by using standard analytical and spectroscopic techniques. These compounds were designed to increase the room temperature excited-state lifetimes of bisterpyridine-type ruthenium(ii) and osmium(ii) complexes. The X-ray crystal structures of two homoleptic complexes 3 and 4 have been determined and show that both the compounds crystallized in orthorhombic form with space group Fddd. The photophysical and redox properties of the complexes have been thoroughly investigated. All the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 6-35 ns. The complexes are found to undergo one reversible oxidation in the positive potential window (0 to +1.6 V) and one irreversible and two successive quasi-reversible reductions in the negative potential window (0 to -2.0 V). The influence of solvents on the photophysical properties of the complexes has also been investigated in detail. The Royal Society of Chemistry 2012.
Perylene-based bis-, tetrakis-, and hexakis(terpyridine) ligands and their ruthenium(II)-bis(terpyridine) complexes: Synthesis and photophysical properties
El-Batal, Hany,Guo, Kai,Li, Xiaopeng,Wesdemiotis, Chrys,Moorefield, Charles N.,Newkome, George R.
, p. 3640 - 3644 (2013)
A series of metallodendrimers 9-11, as well as their corresponding ligands, were designed and synthesized. These materials integrate perylene as a functional core with IItpy> termini; both chromophores are known for their photovoltaic pro
Stimuli-Responsive Molecular Switches and Logic Devices Based on Ru(II)-Terpyridyl-Imidazole Coordination Motif
Deb, Sourav,Sahoo, Anik,Ahmed, Toushique,Baitalik, Sujoy
, p. 8919 - 8931 (2021/08/18)
We report herein the synthesis, photophysics, and electrochemistry of three Ru(II)-terpyridine complexes derived from a new terpyridyl-imidazole ligand (tpy-HImzPh3F2) and study their pH- and temperature-responsive behaviors toward the fabrication of molecular switches. The complexes emitted at room temperature (RT) have a lifetime within the 4.5-49.0 ns domain, depending on the auxiliary ligand and the solvent used. In the acidic region, the complexes exhibit emission, indicating the on-state , while in the basic condition, the emission is totally quenched, indicating the off-state . Similarly, when the temperature is lowered, the emission intensity and lifetime are enhanced, demonstrating the on-state, while increase of temperature leads to quenching of the emission intensity and lifetime, designated as the off-state. In both cases, the process is reversible. The bathochromic shift of the spectral band together with the emission quenching and lowering of the Ru3+/Ru2+ potential is also observed upon deprotonation at elevated pH. In addition, systematic variation of the absorption spectral behaviors upon variation of pH helps in evaluation of the pKa's of the complexes. In essence, the complexes can act as switches emanated from a huge change in their absorption, emission, and redox behaviors as a function of their acidity/basicity (pH) and temperature. Moreover, their emission spectral responses as a function of pH and temperature were utilized for the fabrication of two-input binary logic gates. Density-functional theory (DFT) and time-dependent density-functional theory (TD-DFT) computations are performed for appropriate interpretation of the spectral bands.
Efficient selective oxidation of alcohols to carbonyl compounds catalyzed by Ru-terpyridine complexes with molecular oxygen
Han, Qi,Guo, Xiao-Xuan,Zhou, Xian-Tai,Ji, Hong-Bing
, (2019/11/26)
The oxidation of alcohols with molecular oxygen is a promising approach to produce corresponding carbonyl compounds. In this work, efficient aerobic oxidation of alcohols to carbonyl compounds catalyzed by ruthenium-terpyridine [(tpy-PhCH3)RuCl3] with isobutyraldehyde as co-substrate was developed. Various alcohols including primary and secondary alcohols are smoothly converted to corresponding carbonyl compounds in good yield. In a 100 times large-scale oxidation of benzyl alcohol, benzaldehyde was obtained with 92% isolated yield. Moreover, a plausible mechanism involving high-valence ruthenium species was proposed based on in situ UV–vis spectroscopy.
(Ar-tpy)RuII(ACN)3: A Water-Soluble Catalyst for Aldehyde Amidation, Olefin Oxo-Scissoring, and Alkyne Oxygenation
Joarder, Dripta De,Gayen, Subrata,Sarkar, Rajarshi,Bhattacharya, Rajarshi,Roy, Sima,Maiti, Dilip K.
, p. 8468 - 8480 (2019/07/03)
The synthetic chemists always look for developing new catalysts, sustainable catalysis, and their applications in various organic transformations. Herein, we report a new class of water-soluble complexes, (Ar-tpy)RuII(ACN)3, utilizing designed terpyridines possessing electron-donating and -withdrawing aromatic residues for tuning the catalytic activity of the Ru(II) complex. These complexes displayed excellent catalytic activity for several oxidative organic transformations including late-stage C-H functionalization of aldehydes with NH2OR to valuable primary amides in nonconventional aqueous media with excellent yield. Its diverse catalytic power was established for direct oxo-scissoring of a wide range of alkenes to furnish aldehydes and/or ketones in high yield using a low catalyst loading in the water. Its smart catalytic activity under mild conditions was validated for dioxygenation of alkynes to highly demanding labile synthons, 1,2-diketones, and/or acids. This general and sustainable catalysis was successfully employed on sugar-based substrates to obtain the chiral amides, aldehydes, and labile 1,2-diketones. The catalyst is recovered and reused with a moderate turnover. The proposed mechanistic pathway is supported by isolation of the intermediates and their characterization. This multifaceted sustainable catalysis is a unique tool, especially for late-stage functionalization, to furnish the targeted compounds through frequently used amidation and oxygenation processes in the academia and industry.
