Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands

A series of transition metal complexes involving non-innocent o-dithiolene and o-phenylenediamine ligands has been characterized in detail by various spectroscopic methods like magnetic circular dichroism (MCD), absorption (abs), resonance Raman (rR), electron paramagnetic resonance (EPR), and sulfur K-edge X-ray absorption spectroscopies. A computational model for the electronic structure of the complexes is then proposed based on the density functional theory (DFT) or ab-initio methods, which can successfully account for the observed trends in the experimental spectra (MCD, rR, and abs) of the complexes. Based on these studies, the innocent vs non-innocent nature of the ligands in a given transition metal complex is found to be dependent on the position of the central metal ion in the periodic table, its effective nuclear charge in interplay with relativistic effects.     

Theoretical studies of the spectroscopic properties of blue emitting iridium complexes

Electronic structures, absorptions and emissions of a series of (ppy)₂Ir(acac) derivatives (ppy = 2- phenylpyridine; acac = acetoylacetonate) with fluoro substituent on ppy ligands were investigated theoretically. The ground and excited states geometries were fully optimized at B3LYP/LANL2DZ and CIS/LANL2DZ level, respectively. The HOMO is composed of d(Ir) and π(C^∧N), while the LUMO is localized on C^∧N ligand. The absorptions and emissions in CH₂Cl₂ media were calculated under the TD–DFT level with PCM model. The lowest-lying absorption of these complexes is dominantly attributed to metal-to-ligand and intraligand charge transfer (MLCT/ILCT) transitions and the emission of them originates from ³MLCT/³ILCT excited states. The absorption and emission of these complexes are blue-shifted by increasing the number of fluoro on phenyl, but the spectra are red-shifted by adding fluoro on pyridyl. While a single fluoro of different substituted site on phenyl results in different extent blue-shift to the spectra.     

Synthesis and properties of iridium complexes based 1,3,4-oxadiazoles derivatives

A series of iridium complexes with 2,5-diaryl-[1,3,4]-oxadiazole ligands were synthesized and their electrochemical, photophysical, and electroluminescent (EL) properties studied. It was found that electron-withdrawing or donating substituents on the phenyl ring affected the emission maxima. Complex 3, iridium(III) bis(2,5-bis-(2-hydroxyphenyl)-[1,3,4]oxadiazolato-C²′,N³) (acetyl acetonate), was characterized by single-crystal X-ray structural determination. Three organic light emitting diodes devices were fabricated, which showed stable green-yellow luminescence.     

Synthesis,structure and electrochemical properties of some thiosemicarbazone complexes of iridium

Reaction of thiosemicarbazones of salicylaldehyde and 2-hydroxyacetophenone (H₂L¹ and H₂L²) with [Ir(PPh₃)₃Cl] affords complexes of type [Ir(PPh₃)₂(L)(H)] (L = L¹ or L²) in ethanol. A similar reaction carried out in toluene affords the [Ir(PPh₃)₂(L)(H)] complexes along with complexes of type [Ir(PPh₃)₂(L)Cl], where a chloride is coordinated to iridium instead of the hydride. The structure of the [Ir(PPh₃)₂(L²)(H)] and [Ir(PPh₃)₂(L²)Cl] complexes has been determined by X-ray crystallography. Crystal data for [Ir(PPh₃)₂(L²)(H)]: space group, P2₁/c; crystal system, monoclinic; a=12.110(2) Å, b=17.983(4) Å, c=18.437(4) Å, β=103.42(3)°, Z=4; R ₁=0.0591, wR ₂=0.1107. Crystal data for [Ir(PPh₃)₂(L²)Cl]: space group, P2₁/c; crystal system, monoclinic; a=17.9374(11) Å, b=19.2570(10) Å, c=24.9135(16) Å, β=108.145(5)°, Z=4; R ₁=0.0463, wR ₂=0.0901. In all the complexes the thiosemicarbazones are coordinated to the metal center as dianionic tridentate O, N, S-donors and the two triphenylphosphines are trans. The complexes are diamagnetic (low-spin d? ⁶, S=0) and show intense MLCT transitions in the visible region. Cyclic voltammetry on all the [Ir(PPh₃)₂(L)(H)] and [Ir(PPh₃)₂(L)Cl] complexes shows a quasi-reversible Ir(III)–Ir(IV) oxidation within 0.55–0.78 V vs. SCE followed by an irreversible oxidation of the thiosemicarbazone within 0.91–1.27 V vs. SCE. An irreversible reduction of the thiosemicarbazone is also observed within ?1.10 to ?1.23 V vs. SCE.     

Synthesis,spectroscopic investigations,and biological activity of metal complexes of N-benzoylthiosemicarbazide

N-Benzoylthiosemicarbazide, HL, was obtained by fusion of benzoylhydrazide and ammonium thiocyanate. Reactions of HL with cobalt(II), nickel(II), copper(II), zinc(II), iron(III), cadmium(II), oxovanadium(IV), and dioxouranium(VI) in 1 : 1 molar ratio yield the corresponding complexes. The N-benzoylthiosemicarbazide may act as a neutral or monobasic bidentate ligand coordinated through NS or NO sites. The structures of the HL ligand and its complexes were identified by elemental analysis, infrared, electronic, mass, ¹H-NMR, and ESR spectra as well as magnetic susceptibility and molar conductivity measurements. Different geometries were obtained for the metal complexes. The ligand and its metal complexes were investigated for antibacterial and antifungal properties. Two Gram-positive bacteria, Staphylococcus aureus and Streptococcus pyogenes, two Gram-negative, bacteria, Pseudomonas fluorescens and Pseudomonas phaseolicola and two fungi, Fusarium oxysporum and Aspergillus fumigatus, were used in this study. The metal complexes were more effective than the free ligand.     

Selective electrocatalytic reduction of CO2 to formate by water-stable iridium dihydride pincer complexes

Iridium dihydride complexes supported by PCP-type pincer ligands rapidly insert CO(2) to yield κ(2)-formate monohydride products in THF. In acetonitrile/water mixtures, these complexes become efficient and selective catalysts for electrocatalytic reduction of CO(2) to formate. Electrochemical and NMR spectroscopic studies have provided mechanistic details and structures of key intermediates.     

吸电子基团调控苯基喹啉类铱配合物的合成及光物理性能

以2,2,6,6-四甲基庚二酮(tmd)为辅助配体,2,4-二取代基苯基-4-甲基喹啉(2,4-2R-mpq)为主配体,在主配体中苯基的2位和4位同时引入氟(F)、甲氧基(MeO)或三氟甲基(CF₃),合成出3个铱磷光配合物(2,4-2R-mpq)₂Ir(tmd)(R=F (1)、MeO(2)、CF³(3))。通过元素分析、核磁共振谱和单晶X射线衍射表征了配合物的组成和分子结构。通过紫外可见吸收光谱、光致发光光谱和理论计算对配合物的光物理性能进行了研究。结果表明：3个配合物的晶体均为三斜晶系,空间群均为■,呈稍微扭曲的八面体构型。配合物1、2和3在溶液状态下的发射波长分别为570、582和604 nm,溶液中量子产率分别为96%、80%和80%。在主配体中苯基的2位和4位同时引入F或MeO,配合物电子云发生聚集,而引入CF₃,配合物的电子云分散。与配合物3相比,配合物1和2的发射波长发生了显著的蓝移。     

Synthesis and properties of iridium polymer complexes based on novel bipyridyl ligands

A novel monomer, viz., bipyridyl-containing dicarboxylic acid, was synthesized from 6-pyridyl-3,4-pyridine dicarboxylic acid anhydride and 5-aminoisophthalic acid. Novel polymer macroligands, viz., copolyamides containing 5, 15, 30, and 45% of the bipyridyl side groups, were obtained based on this monomer by low-temperature polycondensation. Metal polymer complexes (MPC) with different Ir(ppy)₂ content were synthesized by the reaction of the polymer ligand with the binuclear complex [Ir(ppy)₂Cl]₂ (ppy is 2-phenylpyridine) and their properties were studied.     

Synthesis and spectroscopic properties of four metal complexes with bipyridinium-based ligand

A series of new transitional metal charge-transfer (CT) complexes with a bipyridinium-based ligand [M(PrBpy)₂(SCN)₄] (M = Cd(II), Ni(II), Co(II)) and [Cu(PrBpy)(SCN)₃(H₂O)] (PrBpyCl = N-(2-pyrazinyl)-4,4′-bipyridinium chloride) have been obtained and determined by X-ray diffraction, FT-IR and elemental analysis. The CT absorption bands of the four compounds were observed by diffuse reflection spectroscopy and a photo-induced electron transfer occurs in methanol solution upon light irradiation.     

Efficient electrochemiluminescent cyclometalated iridium(III) complexes: Synthesis,photophysical and electrochemiluminescent properties

A series of new cyclometalated iridium(III) complexes for electrochemiluminescence (ECL) system were synthesized and fully characterized. Using tri-n-propylamine (TPA) as an oxidative–reductive co-reactant, their ECL properties were studied in acetonitrile (CH₃CN) and mixed CH₃CN/H₂O (50:50, v/v) solutions, respectively. Meanwhile, the influencing factors of ECL efficiencies, including working electrode, pH, and surfactant were investigated. A remarkable ECL enhancement (up to about 13.5 times), in comparison with the commonly used Ru(bpy)₃²⁺ (2,2′-bipyridyl) ruthenium(II), is observed from Ir(FPP)₂(acac) (where FPP is 2-(4-fluorophenyl)-4-phenylpyridine, acac = acetylacetone) at Pt disk electrode. At the same time, an increase in ECL efficiency is also observed in surfactant media. This study provided a new method for further improving and tuning the ECL efficiency by designing new iridium complexes with the appropriate cyclometalated or ancillary ligands.     

Synthesis theoretical and experimental spectroscopic characterization of isoniazid-benzoic acid drug complexes: Insilico and invitro biological evaluations

New organic charge-transfer molecules were synthesised by salt formation from isoniazid and benzoic acid/aspirin compounds acting as acceptor and donor molecules. The synthesised charge transfer complexes were characterized and structurally confirmed by various instrumental techniques such as UV–visible, FT-IR, powder XRD, and NMR spectroscopic methods. Initially, compounds are studied molecular docking analysis with different kinds of proteins, such as 1HNY.pdb, 1PGG.pdb and 4-COX.pdb. Docking results have been compared with molecular electrostatic potential mapping and Mulliken charge distribution methods. Results show that both complexes IAC and IBC have almost the same binding constant value with 1HNY.pdb. Besides, IBC has a more binding constant than the IAC with inflammatory proteins (1PGG.pdb and 4-COX.pdb). The reactivity of the complexes is explained by the chemical potential and electrophilic index derived by the frontier molecular orbitals using the DFT method. These results show a more electrophilic index of IBC than the IAC indicating, more electron affinity nature of IBC. This is also reflected in the in-vitro biological studies, which shows IAC having better activity in anti-diabetic studies whereas IBC has better activity in anti-inflammatory studies. For the sake of complex ability, all biological and molecular docking experimental results are compared with standard drug molecules.     

Mechanistic investigations of imine hydrogenation catalyzed by cationic iridium complexes

Complexes [IrH2(eta6-C6H6)(PiPr3)]BF4 (1) and [IrH2(NCMe)3(PiPr3)]BF4 (2) are catalyst precursors for homogeneous hydrogenation of N-benzylideneaniline under mild conditions. Precursor 1 generates the resting state [IrH2{eta5-(C6H5)NHCH2Ph}(PiPr3)]BF4 (3), while 2 gives rise to a mixture of [IrH{PhN=CH(C6H4)-kappaN,C}(NCMe)2(PiPr3)]BF4 (4) and [IrH{PhN=CH(C6H4)-kappaN,C}(NCMe)(NH2Ph)(PiPr3)]BF4 (5), in which the aniline ligand is derived from hydrolysis of the imine. The less hindered benzophenone imine forms the catalytically inactive, doubly cyclometalated compound [Ir{HN=CPh(C6H4)-kappaN,C}2(NH2CHPh2)(PiPr3)]BF4 (6). Hydrogenations with precursor 1 are fast and their reaction profiles are strongly dependent on solvent, concentrations, and temperature. Significant induction periods, minimized by addition of the amine hydrogenation product, are commonly observed. The catalytic rate law (THF) is rate = k[1][PhN=CHPh]p(H2). The results of selected stoichiometric reactions of potential catalytic intermediates exclude participation of the cyclometalated compounds [IrH{PhN=CH(C6H4)-kappaN,C}(S)2(PiPr3)]BF4 [S = acetonitrile (4), [D6]acetone (7), [D4]methanol (8)] in catalysis. Reactions between resting state 3 and D2 reveal a selective sequence of deuterium incorporation into the complex which is accelerated by the amine product. Hydrogen bonding among the components of the catalytic reaction was examined by MP2 calculations on model compounds. The calculations allow formulation of an ionic, outer-sphere, bifunctional hydrogenation mechanism comprising 1) amine-assisted oxidative addition of H2 to 3, the result of which is equivalent to heterolytic splitting of dihydrogen, 2) replacement of a hydrogen-bonded amine by imine, and 3) simultaneous H delta+/H delta- transfer to the imine substrate from the NH moiety of an arene-coordinated amine ligand and the metal, respectively.     

Rhodium dihydride complexes as models for the theoretical analysis of enantioselective hydrogenation reactions

A combination of molecular mechanics methods and extended Hückel calculations has been applied in order to have access to the more stable complexes expected to be involved as catalytic intermediates in the enantioselective hydrogenation of ketopantolactone (KPL) using chiral aminophosphine-phosphinite (AMPP) chlororhodium complexes. The product selectivity has been deduced from correlations between the prevailing configuration of the hydrogenated derivatives and the energetics of competing diastereomeric dihydride complexes of formula [RhCl(H)₂(AMPP)(KPL)] with the assumption that the enantioselectivity is controlled by the relative energies of such intermediates. The calculations have been obtained from the application of sequential and exhaustive search methodologies. The procedure has been applied to complexes bearing the aminophosphine-phosphinites (S)-Cp,Cp-ProNOP (IV) and (S)-Ph,Cp-ProNOP (V) and bis(aminophosphanes) derived from 2-(anilinomethyl)pyrrolidine (VI–IX). The latter induce a reversal of configuration of the major enantiomer of the hydrogenation product when varying specific substituents at the phosphorus atoms. Computations were carried out also for complexes bearing the two enantiomers (S)- and (R)-Ph,Cp-isoAlaNOP. The lowest energy complexes present enantiomeric structures. A novel insight into the local reactivity of the intermediates has been gained from determining the first migrating hydride according to the superdelocalizability parameter calculated for all isomers. Thus, the configurations of pantolactone arising from the alkoxyrhodium species obtained when assuming a nucleophilic attack of one of the hydrides to the carbonyl group of the ketone has been defined and are in total agreement with the experimental data.     

Mechanistic investigations of imine hydrogenation catalyzed by dinuclear iridium complexes

Treatment of [Ir2(mu-H)(mu-Pz)2H3(NCMe)(PiPr3)2] (1) with one equivalent of HBF4 or [PhNH=CHPh]BF4 affords efficient catalysts for the homogeneous hydrogenation of N-benzylideneaniline. The reaction of 1 with HBF4 leads to the trihydride-dihydrogen complex [Ir2(mu-H)(mu-Pz)2H2(eta2-H2)(NCMe)(PiPr3)2]BF4 (2), which has been characterized by NMR spectroscopy and DFT calculations on a model complex. Complex 2 reacts with imines such as tBuN=CHPh or PhN=CHPh to afford amine complexes [Ir2(mu-H)(mu-Pz)2H2(NCMe){L}(PiPr3)2]BF4 (L = NH(tBu)CH2Ph, 3; NH(Ph)CH2Ph, 4) through a sequence of proton- and hydride-transfer steps. Dihydrogen partially displaces the amine ligand of 4 to form 2; this complements a possible catalytic cycle for the N-benzylideneaniline hydrogenation in which the amine-by-dihydrogen substitution is the turnover-determining step. The rates of ligand substitution in 4 and its analogues with labile ligands other than amine are dependent upon the nature of the leaving ligand and independent on the incoming ligand concentration, in agreement with dissociative substitutions. Water complex [Ir2(mu-H)(mu-Pz)2H2(NCMe)(OH2)(PiPr3)2]BF4 (7) hydrolyzes N-benzylideneaniline, which eventually affords the poor hydrogenation catalyst [Ir2(mu-H)(mu-Pz)2H2(NCMe)(NH2Ph)(PiPr3)2]BF4 (11). The rate law for the catalytic hydrogenation in 1,2-dichloroethane with complex [Ir2(mu-H)(mu-Pz)2H2(OSO2CF3)(NCMe)(PiPr3)2] (8) as catalyst precursor is rate = k[8]{p(H2)}; this is in agreement with the catalytic cycle deduced from the stochiometric experiments. The hydrogenation reaction takes place at a single iridium center of the dinuclear catalyst, although ligand modifications at the neighboring iridium center provoke changes in the hydrogenation rate. Even though this catalyst system is also capable of effectively hydrogenating alkenes, N-benzylideneaniline can be selectively hydrogenated in the presence of simple alkenes.     

Synthesis and characterization of phosphorescent cyclometalated iridium complexes

The preparation, photophysics, and solid state structures of octahedral organometallic Ir complexes with several different cyclometalated ligands are reported. IrCl3.nH2O cleanly cyclometalates a number of different compounds (i.e., 2-phenylpyridine, 2-(p-tolyl)pyridine, benzoquinoline, 2-phenylbenzothiazole, 2-(1-naphthyl)benzothiazole, and 2-phenylquinoline), forming the corresponding chloride-bridged dimers, CwedgeN2Ir(mu-Cl)2IrCwedgeN2 (CwedgeNis a cyclometalated ligand) in good yield. These chloride-bridged dimers react with acetyl acetone (acacH) and other bidentate, monoanionic ligands such as picolinic acid (picH) and N-methylsalicylimine (salH), to give monomeric CwedgeN2Ir(LX) complexes (LX = acac, pic, sal). The emission spectra of these complexes are largely governed by the nature of the cyclometalating ligand, leading to lambda(max) values from 510 to 606 nm for the complexes reported here. The strong spin-orbit coupling of iridium mixes the formally forbidden 3MLCT and 3pi-pi* transitions with the allowed 1MLCT, leading to a strong phosphorescence with good quantum efficiencies (0.1-0.4) and room temperature lifetimes in the microsecond regime. The emission spectra of the CwedgeN2Ir(LX) complexes are surprisingly similar to the fac-IrCwedgeN3 complex of the same ligand, even though the structures of the two complexes are markedly different. The crystal structures of two of the CwedgeN2Ir(acac) complexes (i.e., CwedgeN = ppy and tpy) have been determined. Both complexes show cis-C,C', trans-N,N' disposition of the two cyclometalated ligands, similar to the structures reported for other complexes with a "CwedgeN2Ir" fragment. NMR data (1H and 13C) support a similar structure for all of the CwedgeN2Ir(LX) complexes. Close intermolecular contacts in both (ppy)2Ir(acac) and (tpy)2Ir(acac) lead to significantly red shifted emission spectra for crystalline samples of the ppy and tpy complexes relative to their solution spectra.     

Rhodium and iridium complexes of N-heterocyclic carbenes: Structural investigations and their catalytic properties in the borylation reaction

Bridged and unbridged N-heterocyclic carbene (NHC) ligands are metalated with [Ir/Rh(COD)₂Cl]₂ to give rhodium(I/III) and iridium(I) mono- and biscarbene substituted complexes. All complexes were characterized by spectroscopy, in addition [Ir(COD)(NHC)₂][Cl,I] [COD = 1,5-cyclooctadiene, NHC =  1,3-dimethyl- or 1,3-dicyclohexylimidazolin-2-ylidene] (1, 4), and the biscarbene chelate complexes 12 [(η⁴-1,5-cyclooctadiene)(1,1′-di-n-butyl-3,3′-ethylene-diimidazolin-2,2′-diylidene)iridium(I) bromide] and 14 [(η⁴-1,5-cyclooctadiene)(1,1′-dimethyl-3,3′-o-xylylene-diimidazolin-2,2′-diylidene)iridium(I) bromide] were characterized by single crystal X-ray analysis. The relative σ-donor/π-acceptor qualities of various NHC ligands were examined and classified in monosubstituted NHC-Rh and NHC-Ir dicarbonyl complexes by means of IR spectroscopy. For the first time, bis(carbene) substituted iridium complexes were used as catalysts in the synthesis of arylboronic acids starting from pinacolborane and arene derivatives.     

Phosphorescent binuclear iridium complexes based on terpyridine-carboxylate: an experimental and theoretical study

The phosphorescent binuclear iridium(III) complexes tetrakis(2-phenylpyridine)μ-(2,2':6',2'-terpyridine-6,6'-dicarboxylic acid)diiridium (Ir1) and tetrakis(2-(2,4-difluorophenyl) pyridine))μ-(2,2':6',2'-terpyridine-6,6'-dicarboxylic acid)diiridium (Ir2) were synthesized in a straightforward manner and characterized using X-ray diffraction, NMR, UV-vis absorption, and emission spectroscopy. The complexes have similar solution structures in which the two iridium centers are equivalent. This is further confirmed by the solid state structure of Ir2. The newly reported complexes display intense luminescence in dichloromethane solutions with maxima at 538 (Ir1) and 477 nm (Ir2) at 298 K (496 and 468 nm at 77 K, respectively) and emission quantum yields reaching ~18% for Ir1. The emission quantum yield for Ir1 is among the highest values reported for dinuclear iridium complexes. It shows only a 11% decrease with respect to the emission quantum yield reported for its mononuclear analogue, while the molar extinction coefficient is roughly doubled. This suggests that such architectures are of potential interest for the development of polymetallic assemblies showing improved optical properties. DFT and time-dependent-DFT calculations were performed on the ground and excited states of the complexes to provide insights into their structural, electronic, and photophysical properties.     

Synthesis and properties of electrophosphorescent chelating polymers with iridium complexes in the conjugated backbone

The synthesis of electrophosphorescent chelating polymers by Suzuki polycondensation of A-A- and B-B-type monomers is described, in which the fluorene-alt-carbazole (PFCz) segment is used as polymer backbone. By using alkyl-substituted ligands of iridium complex monomers, chelating copolymers with higher contents of iridium complex can be synthesized. Chemical and photophysical characterization confirm that the Ir complex is incorporated into the polymer backbone as one of the monomer repeat units by means of two 5-bromotolylpyridine ligands. Chelating polymers with Ir complexes in the conjugated polymer backbone show highly efficient energy transfer of excitons from the PFCz host segment to the Ir complex by an intramolecular trapping mechanism. The external quantum and luminous efficiencies of a device made with PFCzMppyIrhm4 copolymer reach 4.1 % ph/el (photons/electron) and 5.4 cd A(-1), respectively, at a current density of 32.2 mA cm(-2), an emission peak of 577 nm, and a luminance of 1730 cd cm(-2). Most important, the devices made from the chelating copolymers show no notable efficiency decay with increasing current density due to reduced concentration quenching and triplet-triplet (T-T) annihilation. This indicates that incorporation of the phosphorescent complex into the rigid conjugated polymer main chain is a new way to simultaneously realize high efficiency, long-term stability, and simple processing of phosphorescent polymer light-emitting diodes.     

Synthesis, structure and electroluminescent properties of cyclometalated iridium complexes possessing sterically hindered ligands

New CN donor ligands incorporating pyridine or benzoimidazole N donors and a sterically hindered cyclometalating aromatic core featuring a polyphenylenephenyl, fluoranthene, or triphenylene segment are prepared and successfully converted into heteroleptic iridium(III) cyclometalated complexes with acetylacetone auxiliary ligands. The X-ray structure of the complex, derived from a ligand containing a fluoranthene fragment, has been solved to unveil the corresponding structure. The results clearly demonstrate that the nature of the sigma-coordinating ligand segment plays a key role in dictating the emission profile and peak position, such that the emission hue has been successfully tuned ranging from green to red. Supplementary support of this viewpoint is also rendered by computational (DFT) approaches. Electroluminescent devices fabricated using a complex as dopant in the PVK matrix were found to exhibit bright greenish yellow emission with promising device characteristics (maximum brightness 26450 cd m(-2) at 30 V and a maximum current efficiency of 40 cd A(-1)).