Heteroleptic Ruthenium Research Articles

Novel heteroleptic ruthenium complexes incorporating 6,7-dichloro-2,3-di(pyridine-2-yl)quinoxaline as polypyridyl bridging ligand: Synthesis, characterization, photophysical, electrochemistry, in vitro biological activity and molecular docking studies

Novel heteroleptic ruthenium complexes incorporating 6,7-dichloro-2,3-di(pyridine-2-yl)quinoxaline as polypyridyl bridging ligand: Synthesis, characterization, photophysical, electrochemistry, in vitro biological activity and molecular docking studies

Application of Novel Ruthenium (II) Polypyridyl Complexes as Robust DNA Probes, Optical Material and Antimicrobials-An Experimental and DFT Approach.

The nature of the interaction of DNA with heteroleptic Ruthenium (II) Polypyridyl complexes of the type [Ru (A)2TPIP]2+, where TPIP = 2-(1-p-tolyl-1H pyrazol-4 -yl)-1H-imidazo [4, 5-f[1. 10] phenanthroline and A = 1,10 phenanthroline (1),4,4'-dimethyl-1,10-ortho Phenanthroline (2),2,2' - bipyridine(3) and 4, 4' dimethyl 2, 2'- bipyridine (4), has been investigated by experimentaland molecular docking approaches. The order of the DNA binding affinities of the synthesised complexes is 1 > 2 > 3 > 4. The findings imply that the unsubstitutedcomplex has a better affinity to bind with DNA than the substituted (dmp and dmb) emphasizing the significance of the auxiliary ligand. Additionally, as the medium's ionic strength drops, the DNA/Ru ratio rises, or when water is displaced by glycerol, the intercalation of complexes into DNA increases. DFT calculations at the B3LYP/LANL2MBlevel was used for molecular geometry (Ground State) and electronic characteristic calculations. The HOMO-LUMO gap of the Ru [II]complex is less than the intercalator and hence kinetically labile. Among the complexes, the bpy complex has shown utmost non-linear optical properties (α = -153.9099 10-24esuand β = 3.8498 10-30esu). The docking study shows the significance of the Metal-intercalator's shorter length may increase DNA binding affinity. This study divulges that the Ruthenium (II) polypyridyl complexes bind to DNA preponderantly by intercalation supporting Viscosity studies. All the complexes have a considerable attraction for guanine. The standarddiskdiffusion method reveals that complexes (1,2,3 and 4) have good antibacterial activity.

Anchor Group Effects in Ruthenium (II) Photosensitizers Bearing N-Heterocyclic Carbene and Polypyridyl Ligands for DSSCs: A Computational Evaluation

In this work, we evaluate the bonding characteristics and interfacial electron transfer dynamics of three heteroleptic ruthenium photosensitizers featuring different terpyridine (tpy) acceptor end configurations through quantum-chemical calculations. These photosensitizers...

Terpyridine Based Heteroleptic Ruthenium Complexes: Influence of Donor and Acceptor Ligands in Photosensitization

AbstractWe report heteroleptic ruthenium complexes of terpyridine (tpy) ligands with directly linked carboxylic acid anchors. These complexes feature methyl or methoxy‐substituted 4′−Phtpy as donor ligands. We prepared these heteroleptic complexes from the ruthenium (II) precursor via a milder route to preclude the homoleptic complex formation. The donor−acceptor arrangement of tpy ligands in these ruthenium complexes renders visible light absorption giving metal and ligand‐to‐ligand charge transfer excitations at c.a. 490 nm. We evaluate the effect of the tpy donor substituents on the light‐harvesting ability in Dye‐Sensitized Solar Cells (DSSCs) and compare their photosensitizing ability with heteroleptic complexes bearing phenyl spacer at the acceptor end. Further, scrutinizing their photovoltaic performance, we studied their electron transfer kinetics in DSSCs using electrochemical impedance spectroscopy. This paper presents the structure‐photosensitization relationship of these heteroleptic ruthenium complexes through a combined experimental and computational approach.

Heteroleptic ruthenium(ii) complexes featuringN-heterocyclic carbene-based C^N donor sets for solar energy conversion

Single isomers of heteroleptic ruthenium(ii) complexes with anN-heterocyclic carbene (NHC)-based C^N donor-set and NCS ligands intransconfigurations are isolated. One of them depicted photovoltaic efficiency of ∼50% of the standardN3dye under similar conditions.

Electrocatalytic water oxidation by heteroleptic ruthenium complexes of 2,6-bis(benzimidazolyl)pyridine Scaffold: a mechanistic investigation.

Three monomeric ruthenium complexes with anionic ligands [RuII(L)(L1)(DMSO)][ClO4] (1), [RuII(L)(L2)(DMSO)] [PF6] (2), and [RuII(L)(L3)(DMSO)][PF6] (3) [L = pyrazine carboxylate, L1 = 2,6-bis(1H-benzo[d]imidazol-2-yl)pyridine, L2 = 4,5-dmbimpy = 2,6-bis(5,6-dimethyl-1H-benzo[d]imidazol-2-yl)pyridine, L3 = 4-Fbimpy = 2,6-bis(5-fluoro-1H-benzo[d]imidazol-2-yl)pyridine, DMSO = dimethyl sulfoxide] as electrocatalysts for water oxidation are reported herein. The single crystal X-ray structure of the complexes reveals the presence of a DMSO molecule, which is supposed to be the labile group undergoing water exchange under the experimental condition of electrocatalysis. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) study shows the appearance of the catalytic wave for water oxidation at Ru(IV/V) oxidation. LSV, CV, and bulk electrolysis technique has been used to study the redox properties of the complexes and their electrocatalytic activity. A systematic variation on the ligand scaffold has been found to display a profound effect on the rate of electrocatalytic oxygen evolution. Electrochemical and theoretical (density functional theory) studies support the O-O bond formation during water oxidation passes through water nucleophilic attack (WNA) for all the ruthenium complexes. At pH 1, the maximum turnover frequency (TOFmax) has been experimentally obtained as 17556.25 s-1, 31648.41 s-1, and 39.69 s-1 for complexes 1, 2, and 3, respectively, from the foot of wave analysis (FOWA). The high value of TOFmax for complex 2 indicates its efficiency as an electrocatalyst for water oxidation in a homogeneous medium.

Participation of fractional charge transfer on the efficiency of singlet oxygen production: Heteroleptic ruthenium (II) bipyridine derivatives

The photophysical properties of some synthesized heteroleptic polypyridyl ruthenium(II) complexes of the form [Ru(bpy)2L](PF6)2 where L = 2,2′-bipyridine, 4,4′-dimethoxy-2,2′-bipyridine, 1,10-phenanthroline, 4,4′-dimethyl-2,2′-bipyridine, 4,7-diphenyl-1,10-phenanthroline and 3,4,7,8-tetramethyl-1,10-phenanthroline, are investigated in acetonitrile. The excited state lifetime of the metal to ligand charge transfer (3MLCT) states of these complex ions are found to be ligand dependent and were found to be in the range 0.56 μs to 1.5 μs. Oxygen quenching of the excited states rate constants, kq, were found to be in the range 1.50–2.24 × 109 M−1s−1. Singlet oxygen quantum yield values, ΦΔ, are found to vary from 0.40 to 0.60 and the efficiency, fΔT, with which excited singlet oxygen, O2 (1Δg), is thereby produced was found to be in the range 0.55–0.85. Treatment of the data with charge transfer and non-charge transfer pathways using Schmidt’s model shows that partial charge transfer parameter was in the range of 0.18 to 0.58. It has also been found that fΔT decreases and oxygen quenching rate constants, kq, increases as pCT increases.

Synthesis, characterization, structural and photophysical properties of heteroleptic ruthenium complexes containing 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand towards electrocatalytic CO2 reduction

Synthesis, characterization, structural and photophysical properties of heteroleptic ruthenium complexes containing 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand towards electrocatalytic CO2 reduction

Chemical and electrochemical water oxidation catalyzed by heteroleptic Ru(III) complexes of anionic 2,6 pyridine dicarboxylate ligand: Experimental and theoretical study

Herein we report two new mononuclear heteroleptic Ruthenium complexes, 1 and 2 with anionic N, O donor pyridine dicarboxylate (pdc2-) ligand along with neutral bipyridine moieties. The general formula of the complexes are [RuIII(pdc2-)(L1)Cl](1), [RuIII(pdc2-)(L2)Cl](2) (Where L1 = bipyridine, L2 = 4,4′-dimethylbipyridine). Synthesis, characterization and water oxidation catalytic properties of both complexes were investigated. A combined theoretical (DFT) and experimental study were carried out to investigate the catalytic (in presence of CAN) and electrocatalytic activity of 1 and 2 for water oxidation in aqueous solution at pH ∼ 1. During electrocatalysis, the catalytic activity wave has been detected in acetonitrile/water 1:9 (v/v) solution in the range 1.39–1.41 V vs SCE. pH based electrochemistry reveals that, water oxidation (at pH = 1) takes place via sequential proton-electron transfer process to form a RuV = O moiety, which oxidises water through I2M pathway. For water oxidation by CAN, both the molecules show appreciably high TOF values 3.47971 x10-4 s−1 and 1.183 × 10–3 s−1 for 1 and 2 respectively in comparison to similar molecules [1,2].

Synthesis and Computational Investigations of Ruthenium(II) Complexes Containing Hydrazine Schiff Base Ligands

Three new heteroleptic ruthenium(II) complexes containing hydrazine schiff base as ligands were synthesized and characterized by using elemental analysis, FT-IR, 1H, 13C NMR, and mass spectroscopic techniques. FT-IR study showed that the substituted phenylhydrazine ligands behave as a monoanionic bidentate O and N donors (L) coordinate to ruthenium via the deprotonated phenolic oxygen and the azomethine nitrogen. They possess excellent thermal stabilities, evident from the thermal decomposition temperatures. Absorption, emission and electrochemical measurements were carried out and the structures of the synthesized complex were optimized using density functional theory (DFT). The molecular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energies, Mulliken atomic charges and molecular electrostatic potential (MEP) of the molecules are determined using B3LYP method and standard 6-311++G (d, p) basis set.

Colorimetric fluoride detection in dimethyl sulfoxide using a heteroleptic ruthenium(ii) complex with amino and amide groups: X-ray crystallographic and spectroscopic analyses.

A bis-heteroleptic ruthenium(ii) complex, [Ru(Hdpa)2(H2pia)]X2 (1·X2; X = Cl, OTf, or F; Hdpa = di-2-pyridylamine; H2pia = 2-pycolinamide; OTf− = CF3SO3−), was synthesized and spectroscopically and crystallographically characterized. The crystal structures of 1·Cl2·2.5H2O and 1·F2·2EtOH revealed essentially identical geometries for the 12+ dication; however, the dihedral angle between the two pyridyl groups in the Hdpa ligands, which represented the degree of bending of the bent conformation, was affected by hydrogen-bonding interactions between the NH group and counterions. In 1·F2·2EtOH, one of the Hdpa ligands had an unusually smaller dihedral angle (15.8°) than the others (29.9°–35.0°). The two NH groups of each Hdpa ligand and the NH2 group of the H2pia ligand in 12+ acted as receptors for F− anion recognition via hydrogen-bonding interactions in a dimethyl sulfoxide (DMSO) solution, and the reaction showed an unambiguous color change in the visible region. Upon the addition of tetra-n-butylammonium fluoride to the red DMSO solution of 1·(OTf)2·H2O, the solution turned dark brown. 1H NMR analysis and absorption spectroscopy of the reaction between 12+ and the added F− anions revealed that the F− anions did not distinguish between the two amino groups of Hdpa and the amide group of H2pia, although they were in different environments in the DMSO solution. A tris-F-adduct with 12+, 1·F3−, was formed when sufficient F− anions were present in the solution, despite the presence of four NH protons in 12+. Time-dependent DFT calculations of 12+ and 1·F3− were consistent with their absorption spectra.

Polynuclear heteroleptic ruthenium(II) photoredox catalysts: Evaluation in blue-light-mediated, regioselective thiol-ene reactions

Polynuclear heteroleptic ruthenium(II) photosensitisers combining either imine or amine-functionalised bipyridyl ligands were synthesised (via Schiff-base condensation/reductive amination reactions), characterised and investigated for their photoreactivity in the hydrothiolation reaction. Furthermore, electrochemical, electronic absorption and emission studies of the complexes were conducted. All the ligand-modified, heteroleptic complexes show red-shifted emission spectra (614–633 nm) relative to the canonical [Ru(bpy)3](PF6)2 complex (609 nm), attributed to the transition from the triplet MLCT excited state (3MLCT) to the ground state. The complexes were evaluated as visible-light photoredox catalysts in the radical hydrothiolation reaction of olefins (thiol-ene coupling) to afford thioethers. Control reactions performed in the absence of the photocatalyst resulted in either significantly lower yields (6%) or no product formation, demonstrating the role of the complexes as photoredox catalysts. The reactions carried out using trinuclear complexes (Ered (Ru2+*/+) = +0.300 V vs Ag/Ag+) resulted in increased yields in comparison with their respective mononuclear congeners and greater than those reported for [Ru(bpy)3](PF6)2, demonstrating the benefits of using polynuclear photocatalysts for photoinitiated redox catalysis reactions.

Synthesis and Study of the Physical and Photovoltaic Properties of Novel Heteroleptic Ruthenium(II) Complexes Ligated with Highly π-Conjugated Bipyridine Ancillary and Phenanthroline Anchoring Ligand for Dye-Sensitized Solar Cells

Six new heteroleptic ruthenium(II) complexes (JM1–JM6), each bearing a highly π-conjugated bipyridine ancillary ligand (a methoxy-substituted analog (L1) and a phenanthroline-type anchoring ligand (L2) (dcphen or dcvphen; [Ru(L)2(NCS)2][TBA]2; L1 = 4,4′-bis{2-(3,4-dimethoxyphenyl)ethenyl}-2,2′-bipyridine (dmpbpy), 4,4′-bis{2-(1,1′-biphenyl)-4-ylethenyl}-2,2′-bipyridine (bpbpy), or 4,4′-bis{2-(4′-methoxy-[1,1′-biphenyl]-4-ylethenyl}-2,2′-bipyridine (mbpbpy); L2 = 4,7-dicarboxy-1,10-phenanthroline (dcphen) or 4,7-bis(E-carboxyvinyl)-1,10-phenanthroline (dcvphen)) were synthesized, and their physical and photovoltaic properties were investigated. Various dye-sensitized solar cells (DSSCs) were fabricated using heteroleptic ruthenium(II) complexes. Ruthenium(II) complex JM1, ligated to dmpbpy (ancillary) and dcphen (anchoring) ligands, exhibited the maximum power conversion efficiency (PCE) value of 3.40%, which was approximately 71% of the efficiency exhibited by the commercially available N719-sensitized solar cells. Ruthenium(II) complex JM5, ligated to mbpbpy (ancillary) and dcphen (anchoring) ligands, exhibited the second-best PCE value (2.52%), and ruthenium(II) complex JM3, ligated to bpbpy (ancillary) and dcphen (anchoring) ligands, exhibited a PCE value of 1.45%. It was observed that the PCE values of the DSSCs could be significantly improved by introducing the electron-donating methoxy group at proper positions of the ancillary ligands present in the heteroleptic ruthenium(II) complexes (such as JM1 and JM5).

Light‐Induced Ejection of a Tridentate Ligand from a Ruthenium(II) Complex

AbstractA new heteroleptic ruthenium complex based on a 2,2′;6′,2′′‐terpyridine (tpy) and a thioether‐based tridentate ligand, btap (btap: 2,6‐bis(2‐thioanisyl)pyridine) was synthesized. Under visible light irradiation, this complex in solution in acetonitrile undergoes a photochemical ejection of the thioether ligand leading to [Ru(tpy)CH3CN)3]2+ and the free ligand. The reaction was monitored using NMR and UV‐Vis spectroscopies. This is very probably the first example of a tridentate ligand being expelled by the action of light.

Synthesis of benzimidazole moiety heteroleptic ruthenium complex and use as sensitizer in dye-sensitized solar cells

Synthesis of benzimidazole moiety heteroleptic ruthenium complex and use as sensitizer in dye-sensitized solar cells

Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis.

Ruthenium(II) polypyridine complexes are among the most popular sensitizers in photocatalysis, but they face some severe limitations concerning accessible excited-state energies and photostability that could hamper future applications. In this study, the borylation of heteroleptic ruthenium(II) cyanide complexes with α-diimine ancillary ligands is identified as a useful concept to elevate the energies of photoactive metal-to-ligand charge-transfer (MLCT) states and to obtain unusually photorobust compounds suitable for thermodynamically challenging energy transfer catalysis as well as oxidative and reductive photoredox catalysis. B(C6F5)3 groups attached to the CN– ligands stabilize the metal-based t2g-like orbitals by ∼0.8 eV, leading to high 3MLCT energies (up to 2.50 eV) that are more typical for cyclometalated iridium(III) complexes. Through variation of their α-diimine ligands, nonradiative excited-state relaxation pathways involving higher-lying metal-centered states can be controlled, and their luminescence quantum yields and MLCT lifetimes can be optimized. These combined properties make the respective isocyanoborato complexes amenable to photochemical reactions for which common ruthenium(II)-based sensitizers are unsuited, due to a lack of sufficient triplet energy or excited-state redox power. Specifically, this includes photoisomerization reactions, sensitization of nickel-catalyzed cross-couplings, pinacol couplings, and oxidative decarboxylative C–C couplings. Our work is relevant in the greater context of tailoring photoactive coordination compounds to current challenges in synthetic photochemistry and solar energy conversion.

Synthesis, Crystal Structure, and Photophysical Properties of Heteroleptic Ruthenium(II) Complexes with Functionalized Diimine Ligands

Synthesis, Crystal Structure, and Photophysical Properties of Heteroleptic Ruthenium(II) Complexes with Functionalized Diimine Ligands

Dye sensitized solar cell-based optoelectronic device using novel [Ru(L1)(L2)(NCS)2] complex

A dye sensitized solar cell-based photodiode was prepared using novel [Ru(L1)(L2)(NCS)2] complex for solar energy and optoelectronic applications. The new heteroleptic ruthenium(II) complex [Ru(L1)(L2)(NCS)2], was synthesized from the reaction of (pyridyl)benzimidazole ligands. The possible usage of [Ru(L1)(L2)(NCS)2] complex in dye synthesized solar cell-based photodiode was investigated using electrical and capacitance characteristics. The device was irradiated under various solar light intensities. The change in photocurrent of the device confirms the photoconducting behavior of prepared device. The device exhibited both the photocapacitance and photoresponse behavior with solar illumination. The obtained optoelectrical results suggest that the studied photodiode with [Ru(L1)(L2)(NCS)2] complex could be used in optoelectronic device for optical switching and controlling applications.

Heteroleptic Ruthenium(II) Complexes with 2,2'-Bipyridines Having Carbonitriles as Anchoring Groups for ZnO Surfaces: Syntheses, Physicochemical Properties, and Applications in Organic Solar Cells.

Heteroleptic ruthenium (II) complexes were used for sensitizing ZnO surfaces in organic solar cells (OSCs) as mediators with photoactive layers. The complexes [Ru(4,4'-X2-bpy)(Mebpy-CN)2]2+ (with X = -CH3, -OCH3 and -N(CH3)2; bpy = 2,2'-bipyridine; Mebpy-CN = 4-methyl-2,2'-bipyridine-4'-carbonitrile) were synthesized and studied by analytical and spectroscopical techniques. Spectroscopic, photophysical, and electrochemical properties were tuned by changing the electron-donating ability of the -X substituents at the 4,4'-positions of the bpy ring and rationalized by quantum mechanical calculations. These complexes were attached through nitrile groups to ZnO as interfacial layer in an OSC device with a PBDB-T:ITIC photoactive layer. This modified inorganic electron transport layer generates enhancement in photoconversion of the solar cells, reaching up to a 23% increase with respect to the unsensitized OSCs. The introduction of these dyes suppresses some degradative reactions of the nonfullerene acceptor due to the photocatalytic activity of zinc oxide, which was maintained stable for about 11 months. Improving OSC efficiencies and stabilities can thus be achieved by a judicious combination of new inorganic and organic materials.

Chiroptical switching behavior of heteroleptic ruthenium complexes bearing acetylacetonato and tropolonato ligands.

Four types of tris-chelate ruthenium complexes bearing acetylacetonato (acac) and tropolonato (trop) ligands were synthesized and optically resolved into Δ and Λ isomers: [Ru(acac)3] (Ru-0), [Ru(acac)2(trop)] (Ru-1), [Ru(acac)(trop)2] (Ru-2), and [Ru(trop)3] (Ru-3). Chiral HPLC chromatograms, electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) of the four ruthenium complexes were systematically investigated. As a result, the absolute configurations of the newly prepared enantiomeric complexes Ru-2 and Ru-3 were determined. For the case of Ru-2, its absolute configuration was also confirmed by single crystal X-ray diffraction analysis. The ECD changes upon chemical oxidation were further investigated for the four complexes. An ECD change in enantiomeric Ru-1 was observed upon oxidation, but the oxidized species soon returned to the neutral state within a few minutes. Enantiomers of Ru-3 also showed explicit ECD changes upon oxidation. Further, the lifetime of the oxidized state was the longest among the four investigated complexes, whereas they racemized in solution at room temperature. In contrast, the enantiomers of heteroleptic complexes (Ru-1 and Ru-2) concurrently exhibited ECD changes, relatively long lifetime of the oxidized state, and nil or quite slow racemization behavior. The coexistence of acac and trop ligands was key to making the competing factors compatible in the resultant ruthenium complexes.