The reaction of the pentaosmium cluster Os5C(CO)15 (1) with the diphosphine (Z)-Ph2PCHCHPPh2 (dppen) has been studied over the temperature range 328–358 K. Diphosphine addition to Os5C(CO)15 yields the arachno cluster Os5C(CO)15(κ1-Peq-dppen) (2) as the initially observed product. Cluster 2 transforms to the arachno cluster Os5C(CO)14(κ2-Peq,Peq-dppen) (3) upon CO loss and chelation of the pendent phosphine moiety. The loss of a second CO in cluster 3 is accompanied by polyhedral contraction to give the square pyramidal nido cluster Os5C(CO)13(κ2-Pa,Pb-dppen) (4). Clusters 2–4 were characterized in solution by IR and NMR spectroscopies, and the molecular structure of each new cluster was established by X-ray crystallography. The kinetics for the formation of 2 from 1 and dppen support a bimolecular process involving dppen addition to 1 analogous to the reported ligand additions to the family of M5C(CO)15 clusters (where M = Fe, Ru). Cluster 2 is labile and serves as the precursor to 3 + CO, which undergoes conversion to 4 + CO. The kinetics for these reactions have been explored, and these data, in conjunction with DFT calculations, have provided mechanistic insight into the stepwise conversion of 1 and dppen to 4 + 2CO.

Three different imidazolylidene ligand precursors with methyl groups in 4- and 5-position were synthesized and selected to build a series of nine cyclometalated platinum(II) complexes. Next to the carbene ligands, β-diketonate and bis(pyrazolyl)borate motifs were used as auxiliary ligands. All complexes were fully characterized by standard techniques, five of them also by solid-state structure determinations. All of the synthesized platinum complexes show phosphorescence at room temperature in a PMMA matrix with quantum yields of up to 92% in the green-blue to pure blue area (CIE color coordinates of 0.154; 0.119) of the visible spectrum. Quantum chemical calculations (PBE0/6-311G*) as well as electrochemical experiments provided additional insight into the properties of these compounds.

In this work, systematical comparisons are performed between two Ir-complex based electron donor materials. Compared to the control TBzIr with alkylterthiophene coupled benzo[d]thiazole as cyclometalated ligand, the new-developed TBzRIr is designed by attaching additional strong electron-accepting dicyanorhodanine endcaps to the main ligands. The enlarged ligand conjugation length and amplified intraligand donor-acceptor interactions induces TBzRIr to show less efficient spin-orbital coupling with obviously weakened triplet emission and shorter triplet lifetimes than TBzIr. Notably, TBzRIr demonstrates beneficial physical parameters for organic solar cells with deeper energy levels, remarkably enhanced light-harvest capacity and visibly increased neat-film hole mobility than TBzIr. However, TBzRIr conversely yields inferior device efficiency than TBzIr in the corresponding organic solar cells, with sharply decreased power conversion efficiency from 5.36% for TBzIr:Y6 to 3.05% for TBzRIr:Y6. Besides on the influence of improved film morphologies for TBzIr:Y6, the benefits of stronger triplet feature of TBzIr is also expected to facilitate exciton dissociation, suppress charge recombination, and thus to enhance photovoltaic performance.

A new series of heterotrinuclear complexes of the type [Ru(dppm)2((CCC6H4CCC6H3 (O)HCNC6H4X)Ni(L'))2] (1a-c) and [Ru(dppm)2((CCC6H4CCC6H3(O)HCNC6H4X)Zn(L'))2] (2a-c) were prepared by the reaction of trans-[Ru(dppm)2(CCC6H4CCC6H3(OH)HCNC6H4X)2] with Ni(II)/Zn(II) ions in presence of 8-hydroxyquinoline. (where, X= Cl, Br, I; L'= 8-hydroxyquinoline) All the complexes were characterized by elemental analysis, FT-IR, 1H NMR, ESI-MS, UV–visible and thermogravimetric studies. The electrochemical properties of all the complexes indicate quasireversible redox behaviour corresponding to Ru(II)-Ru(III) and Ni(II)/ Ni(III) for 1a-c and Ru(II)/Ru(III) for 2a-c and are susceptible to variation of substituent group on ligand. All complexes show room temperature luminescence corresponding to π→π* intraligand charge transfer (ILCT) transition. The emission wavelength of the complexes is finely tuned by increasing π-conjugation and variation of substituent groups in the complexes. The second harmonic generation (SHG) efficiency of the complexes was measured by Kurtz-powder technique indicating that all complexes displayed the second harmonic generation (SHG) property.

Reactions of arene d6 platinum group metal dimers [(arene)MCl2]2 (where M =Ru/Rh/Ir and arene = p-cymene, Cp*) with thiourea derivatives L1 {2-(3-methoxybenzoyl)-N-phenylhydrazinecarbothioamide}, L2 {2-benzoyl-N-phenylhydrazinecarbothioamide} and L3 {N-phenyl-2-(thiophene-2-carbonyl)hydrazinecarbothioamide} yielded a series of mononuclear neutral complexes (1-9) formulated as [(arene)M(L)к2(N∩S)Cl] {where L=L1, L2, L3, M =Ru, Ir, arene = p-cymene, Cp*} and [Cp*Rh(L)к1(S)Cl2] {where L=L1, L2, L3}. Further, treatment of monodentate rhodium complexes with sodium azide resulted in interesting dinuclear sulfur bridged complexes (10-12). These complexes have been characterized by various spectroscopic techniques such as FT-IR, UV-Vis, NMR spectroscopy and ESI-Mass spectrometry. The solid-state structures of the representative complexes determined by single-crystal X-ray diffraction studies showed that the ligands exhibit versatile coordination modes. In vitro antibacterial activity was evaluated against human pathogenic bacteria by the agar well diffusion method, which revealed their significant activity against both Gram-positive (Staphylococcus aureus and Bacillus thuringiensis) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. Furthermore, antioxidant activity by DPPH assay revealed that the ligands and complexes are potent antioxidants.

During a 50 years history of Organometallic Chemistry, the author - a former Regional Editor of the Journal of Organometallic Chemistry - and his Regensburg, Frankfurt, and Munich research groups contribuited to the shaping and progress of ths field which became more and more interdisciplinary ever since. Thus, akey discovery was the power and verstility of N-heterocyclic carbenes as highly activating and versatile novel catalysts ligands in various carbon-carbon bond-forming reactions, particularly olefin metathesis and Heck-type reactions. Other disseminating research contributions cover metal-metal multiple bonds, dimetallacyclopropanes, orgaometal oxides, water-soluble catalysts for the industrial hydroformylation, and metal alkoxides including organolanthanoids for CVD-processes.

The cancer stems from the unregulated proliferation and growth of cells in different organs or tissues throughout the body, is one of the most common and difficult to treat, deadly diseases of the century. While photodynamic therapy (PDT) method was primarily used in the treatment of cancer disease, sonodynamic therapy (SDT) method was then utilized as an alternative solution and finally sono-photodynamic therapy (SPDT) treatment was developed as the combination of these two therapeutic methods. Ultrasound waves have the ability to penetrate deep into tissues, allowing SDT and SPDT to reach and treat tumors located in deeper regions. The importance of these studies lies in their potential for non-invasive treatment, enhanced therapeutic efficacy, selective targeting, develop novel photosensitizers, deep tissue treatment, versatility in combination therapy, and their contribution to research and development in the field of therapeutic ultrasound and PDT. Today, the use of phthalocyanine complexes, known as sensitizers that can produce high amounts of reactive oxygen, is becoming increasingly important in these therapeutic methods. To achieve this objective, a novel silicon phthalocyanine derivative with bromo-naphthoxy substitution was synthesized and subjected to characterization through various spectroscopic methods including elemental analysis, FT-IR, UV-Vis, MALDI-TOF MS, and 1H-NMR. Photophysical, photochemical and sono-photochemical properties of the new complex were studied and analyzed. While the singlet oxygen efficiency in PDT method was found as ФΔ=0.78 in DMSO, ФΔ=0.69 in DMF, it was figured out in SPDT method as ФΔ=0.94 in DMSO and ФΔ=0.81 in DMF. This data shows that the new phthalocyanine compound is a good photosonosensitizer candidate that can be used in both PDT and SPDT methods.

Methods to synthesize diphosphines with different substituents on the two phosphorus centers are limited, particularly for the synthesis of unsymmetric bis(dialkylphosphine) ligands. Herein is reported a modular and high-yielding synthesis of borane-protected unsymmetric 1,3-bis(diphosphino)propanes containing either two dialkylphosphine moieties or one dialkylphosphine and one diphenylphosphine group. The method relies on sequential phosphine substitution on 1,3-dibromopropane. The borane-protected diphosphines are readily converted to bis(phosphonium salts), which serve as convenient preligands. Palladium(II) complexes of di-tert-butyl(3-(dicyclohexylphosphino)propyl)phosphine (tBuCyPP), di-tert-butyl(3-(diisobutylphosphino)propyl)phosphine (tBuiBuPP), and diisobutyl((3-(dicyclohexylphosphino)propyl)phosphine (CyiBuPP) have been prepared. The tBuiBuPP and CyiBuPP complexes have been structurally characterized and their structural properties compared to symmetric (1,3-diphosphinopropane)palladium dichloride structures.

The capacity to broaden the range of molecular weights displayed by polyolefinic materials is an important factor to be considered in the design of polymerization catalysts. Herein, the 2,6-dibenzhydryl-4-trifluoromethoxy modified bis(imino)pyridyl-ferrous chlorides, [2-[CMeN{2,6-{(C6H5)2CH}2-4-(F3CO)C6H2}]-6-(CMeNAr)C5H3N]FeCl2 [Ar = 2,6-Me2C6H3 Fe1, 2,6-Et2C6H3 Fe2, 2,6-i-Pr2C6H3 Fe3, 2,4,6-Me3C6H2 Fe4, 2,6-Et2-4-MeC6H2 Fe5], are used as precatalysts in the solution polymerization of ethylene. On the activation with either MAO or MMAO, all complexes displayed high productivity [up to 18.4 × 106 g (PE) mol-1 (Fe) h-1 for Fe5/MAO], generating highly linear polyethylenes with a wide range of molecular weights (Mw range: 0.85 × 103 to 8.80 × 105 g mol-1). Notably, higher activity was achieved in hexane than in toluene under MAO activation, while the opposite trend was seen with MMAO, highlighting the key role played by solvent in the polymerization process. By comparison with structurally related iron catalysts, the presence of the electron withdrawing para-trifluoromethoxy group has the effect of increasing the molecular weight of the polyethylene. In addition to the polymerization studies, full synthetic and characterization details are presented for Fe1-Fe5 including the X-ray structures of Fe1 and Fe2.

The palladium-catalyzed uncaging of alloc-protected amines in living cells has been extensively studied mostly in the form of nanostructures or mesostructures. However, the scarcity of kinetic and mechanistic studies of discrete palladium complexes for deallylation reactions has hindered progress. Herein, we report the development of a series of discrete palladium complexes bearing acetanilide ligands, which exhibit a good balance between reactivity and stability in living cells. We investigated the catalytic activity and cytotoxicity of these complexes in SiHa cells and found that acetanilide[tri(2-furyl)phosphine]palladium(II) triflate showed promising results. Under physiological conditions, this palladium complex exhibited a second-order reaction rate of 30 M−1 s−1, and liquid chromatography-mass spectrometry (LC-MS) studies suggested the possibility of a tandem Heck/Tsuji-Trost mechanism. Our results demonstrate the potential of using these discrete palladium complexes for bioorthogonal chemistry studies in living cells.

This account briefly summarizes the organometallic chemistry of technetium over the thirty years of experience made by the author and others. Earlier publications, many from the "Journal of Organometallic Chemistry", are included as well for showing that a careful reading of the "old" literature may influence actual chemistry, challenges and concepts, and the author's own research in particular. It is shown that kinetic differences between 99Tc and 99mTc lead to complexes not immediately envisaged under specific reaction conditions, but are very useful for ultimate application in molecular imaging and bioorganometallic chemistry. As with many other d-elements, most of the organometallic chemistry is based on a few starting materials, e.g. binary carbonyls such as Tc2(CO)10, which is hardly available nowadays for different reasons. Still, there are ways around it to get to the same compounds as when starting from Tc2(CO)10. Organometallic technetium chemistry, a niche field, is still underdeveloped which is mirrored by the fact that some important core organometallics such as η2-alkene and η2-alkyne complexes, standard for other d-elements, are still missing.

Versatile nature of zirconium (IV)based metal-organic frameworks makes them an attractivecandidate for many applications such as catalysis, energy storage, gas separation, etc., due to their high chemical, mechanical and thermal stability, and high porosity. Batch-wise synthesis incurs extra costs and time while restricting reaction control and structural tunability with precision control for customized crystal sizes. Here, we synthesize zirconium-based MOF-808 under three distinct operating conditions: continuous microfluidic synthesis, microwave-assisted, and ultrasound-assisted synthesis. Zirconium-based MOF-808 has been synthesized in green solvents - water and ethanol at a constant metal salt:ligand ratio of 3:1 (Zr:BTC). These synthesis approaches have been demonstrated,and MOF-808 samples were analyzed using sophisticatedanalytical techniques, including field emission scanning electron microscopy (FE-SEM), Powder X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) analysis and Fourier transform infrared spectroscopy (FTIR). Analysis results show that the microfluidics approach exhibits good results among all others in terms of morphology, surface area, and thermal stability from all three approaches. This paper provides new avenues of synthesis approach routes on a lab-scale environment that is a first step toward the switch to more effective MOF synthesis approaches at the industrial scale.

A Copper(II) Schiff-base complex immobilized mesoporous silica-41 (Copper-Schiff base@MCM-41) was synthesized using the ultrasonication method. The formation of material with expected morphological and structural features was confirmed with various characterization techniques including UV-DRS, FTIR, LXRD, SEM, EDAX, ICP-AES, HR-TEM, BET, TGA-DTA, and ESR analyses. Furthermore, the Copper-Schiff base@MCM-41 catalyzed Biginelli reaction has performed under an eco-friendly solvent approach at room temperature, achieving high product yield. After the completion of the reaction, the catalyst was easily recovered using the filtration method and reused for another reaction, maintaining comparable product yield up to five repetitive cycles without any major catalytic activity decay. The exhibition of excellent catalytic activity towards 3,4-dihydropyrimidone derivatives with high product yield in a short time at room temperature proved that the Copper-Schiff base@MCM-41 is a more effective heterogeneous catalyst toward the Biginelli reaction compared to other catalysts. The plausible reaction mechanism has proposed based on the study.

Phthalocyanine compounds display strong absorbance during their interaction with light thanks to the delocalized π bonds. In recent years, the studies have been carried out to use phthalocyanine compounds, which are sensitive to light, as photosensitizers in the singlet oxygen production.In present work, two different phthalonitrile derivatives were separately obtained as a result of the reaction of 3-nitrophthalonitrile and 4-nitrophthalonitrile compounds with 2-hydroxymethyl-1,4-benzodioxane. As a result of the reaction of these phthalonitrile derivatives with gallium(III) metal ion, non-peripherally and peripherally 2-hydroxymethyl-1,4-benzodioxane substituted gallium(III) phthalocyanines (3-GaPc and 4-GaPc) were separately obtained. The synthesis of the compounds was performed by conventional methods and the characterization processes were carried out using ultraviolet and visible light (UV-Vis) absorption spectroscopy, infrared (IR) spectroscopy, proton nuclear magnetic resonance (1H-NMR) spectroscopy and matrix assisted laser desorption/ionization mass spectroscopy (MALDI-TOF-MS) methods. Photophysical, photochemical and aggregation properties of two gallium(III) phthalocyanine compounds were investigated in different solvents such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and toluene solvents for their usability in singlet oxygen generation. Solvents have an effect on the results. The result show that these compound display good solubility and suitable singlet oxygen generation properties in the mentioned solvents.

Alzheimer's disease (AD) is one of the irreversible neurodegenerative disorders among older people and causes behavior, memory and thinking problems. In this study, peripheral tetra-[(6-(3-(diethylaminophenoxy)hexyl]oxy) substituted zinc (II) and nickel (II) phthalocyanines and their water soluble derivatives were prepared for the first time. To determine the potential of novel synthesized compounds to be used in Alzheimer's disease (AD), in vitro and in silico AChE/BuChE inhibitory and cytotoxic effects were investigated. The docking scores and ∆G values clearly indicated a stronger affinity between DE-C6-CN and AChE than BuChE. In addition, DE-C6-ZnQ and DE-C6-NiQ had higher inhibitory effects than galantamine and both compounds were competitive inhibitors on AChE and BuChE according to Lineweaver-Burk plots. DE-C6-NiQ had a more potent cytotoxicity effect than DE-C6-ZnQ in SH-SY5Y cells. All these results indicated that DE-C6-ZnQ had the potential to be used in the treatment of AD.

Two ionic liquids (3-(3‑chloro-2-hydroxypropyl)-1-vinyl-1H-imidazol-3-ium chloride and 3-(3‑chloro-2-hydroxypropyl)-1‑butyl‑1H-imidazol-3-ium chloride) were prepared from commercially available, inexpensive 1-vinyl imidazole or 1‑butyl imidazole, respectively, in ethanol at room temperature. Then, these ionic liquids were treated with PPh2Cl to obtain ionic liquid-based phosphinite ligands and the reaction of these phosphinites with [Ru(η6-benzene)(μ-Cl)Cl]2, [Ru(η6−p-cymene)(μ-Cl)Cl]2, or [Ir(η5-C5Me5)(μ-Cl)Cl]2 gave the corresponding ruthenium and iridium complexes. Structures of the synthesized compounds were clarified by multinuclear NMR and IR spectroscopy as well as microanalysis. Furthermore, the complexes were applied as catalysts in the transfer hydrogenation of acetophenone derivatives to afford the corresponding alcohols with high conversions. Notably, [Ru(Ph2POC8H11N2Cl2)(η6-benzene)Cl2] acts as a good catalyst, giving the corresponding alcohols in 97–98% yields in 15 min at 82 °C (TOF ≤ 400 h−1) for the transfer hydrogenation reaction in comparison to analogous complexes. The catalysts are also useful for a variety of related ketone substrates with various electronic and steric regulating groups.

The purpose of this study is to investigate the magnetic and electrochemical properties of the new GO/Pani-CeO2/CoFe2O4 nanocomposite. This nanocomposite was synthesized through two routes and the results of the investigations show interesting cases. The interaction between CeO2-Pani and the presence of Ce-O was confirmed by FTIR spectroscopy and the XRD data showed the successful formation of the magnetite nanoparticles with the presence of CeO2 anchored onto polyaniline within the GO matrix. X-ray photoelectron spectroscopy (XPS) showed well the presence of Ce+3 (in addition to Ce+4) and its percentage. The products were identified by other methods such as VSM, FE-SEM, and EDX. Electrochemical studies such as cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) measurements, and electrochemical impedance spectroscopy (EIS) to evaluate the effect of changes in the accumulation type of the synthesized nanocomposite were recorded in 0.5 M H3PO4 vs. Ag/AgCl. The stability test also shows that the desired compound has relatively good stability as a supercapacitor.

The production of cyclohexane oxidation to cyclohexanol and cyclohexanone (KA oil) in the chemical industry is still constrained by low conversion, low selectivity, and drastic reaction conditions. To address this, we have developed MoO3-x ultrafine nanorods-Au nanoparticles composite by in situ uniform growth for the boosted photocatalytic oxidation of cyclohexane. The resulting MoO3-x-Au Schottky heterojunction possesses significantly improved catalytic performance in cyclohexane oxidation, achieving a conversion rate of 9.99% and the KA oil selectivity of 96.37%. Using the Finite-Difference Time-Domain (FDTD) method, we interpreted the enhanced electric field distribution of the composite. Moreover, the photocatalytic mechanism was validated by H2O2 production and in-situ FTIR characterization. The adsorption experiments validated that the high selectivity of KA oil is originated from the superior adsorption capability of MoO3-x-Au for cyclohexane over cyclohexanol and cyclohexanone. Our study showcases the potential of MoO3-x ultrafine catalysts in the green synthesis of industrial organic chemical products.

The geometries and energetics of binuclear hexamethylbenzene manganese carbonyls (Me6C6)2Mn2(CO)n (n = 4, 3, 2, 1), including the experimentally known tetracarbonyl, have been examined using density functional theory. Relatively low- energy structures include trans- and cis-(η6-Me6C6)2Mn2(CO)2(µ-CO)2 doubly bridged tetracarbonyl structures and a triplet (η6-Me6C6)2Mn2(µ-CO)3 triply bridged structure analogous to experimentally known isoelectronic binuclear cyclopentadienyliron carbonyls. However, in addition, a series of low-energy quintet spin state structures(η10–2n-Me6C6)Mn(CO)n–Mn(η6-C6Me6) (n = 4, 3, 2) is found. The tetracarbonyls and tricarbonyl of this series have partially bonded hexamethylbenzene rings suggesting a certain fragility of the hexamethylbenzene-manganese linkage not found in the isoelectronic cyclopentadienyliron compounds. For the dicarbonyl and monocarbonyl (Me6C6)2Mn2(CO)n (n = 2, 1) systems, singlet structures having the triple or quadruple manganese-manganese bonds necessary to give each manganese atom the favored 18-electron configuration are very high-energy structures relative to isomeric triplet and quintet spin state structures.

The alkenyl- and thiolate-bridged diiron carbonyl complexes [Fe2(μ-SC6H4CR1CH)(CO)6] (R1 = H or Me), which are derived from [Fe3(CO)12] and benzothiophenes, reacted with alkynes (R2CCR3) under photoirradiation conditions to form the acyl complexes [Fe2{μ-SC6H4CR1CHCR2C(R3)CO}(CO)5]. In this reaction, an alkyne and CO are inserted into the Fe–alkenyl bond, and the bulky substituents of alkynes, including a redox active ferrocenyl group, occupy the R3 position. To elucidate the reaction pathway, the reaction of the in situ generated acetonitrile complex [Fe2(μ-SC6H4CHCH)(CO)5(NCCH3)] with ethynylbenzene was monitored by 1H NMR spectroscopy. The results demonstrated that the acetonitrile complex undergoes facile insertion of the alkyne, which is followed by CO insertion to give the corresponding acyl complex [Fe2{μ-SC6H4(CH)3C(Ph)CO}(CO)5]. The reactivity of the bridging alkenyl moiety is related to the dynamic behavior of the alkenyl-thiolate ligand (SC6H4CHCH)2- as well as the entering alkyne. Temperature dependent 31P NMR measurements of the dmpm-bridged complex [Fe2(μ-SC6H4CHCH)(μ-dmpm)(CO)4] (dmpm = bis(dimethylphosphino)methane) revealed that the activation parameters for the flip-flop motion of the alkenyl-thiolate ligand are ΔH‡ = 46.7(7) kJ mol-1 and ΔS‡ = −46(2) J mol-1 K-1.