Co-Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO2 for Catalytic Hydrogenation of Cinnamaldehyde.

Transition-metal-doped black titania, primarily in the anatase phase, shows promise for redox reactions, water splitting, hydrogen generation, and organic pollutant removal, but exploring other titania phases for broader catalytic applications is underexplored. This study introduces a synthetic approach using a Co-Ti bimetallic complex bridged by a 1,10-phenanthroline-5,6-dione ligand as a precursor for the synthesis of cobalt-doped black titania [Co@L2N@b-TiO2]. The synthesis involves precise control of pyrolysis conditions, yielding a distinct structure dominated by the rutile phase over anatase, with active cobalt encapsulated within a nitrogen-doped graphitic layer, primarily as Co0 rather than CoII and CoIII. The synthesized material is employed for the selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) under industrially viable conditions. The efficiency and selectivity of Co@L2N@b-TiO2 was compared with other catalysts, including cobalt-doped rutile TiO2 (Co@r-TiO2), anatase TiO2 (Co@a-TiO2), and black titania (Co@b-TiO2) as well as materials pyrolyzed under different atmospheres and temperatures, materials with phenanthroline ligands, and materials lacking any ligands. The superior performance of Co@L2N@b-TiO2 is attributed to its high surface area, stable Co0 within the nitrogen-doped graphitic layer, and composition of rutile and anatase phases of TiO2 and Ti2O3 (referred to as RAT), along with the synergistic interaction between RAT and Co0. These factors significantly influence the efficiency and selectivity of COL over hydrocinnamaldehyde (HCAL) and hydrocinnamyl alcohol (HCOL), indicating potential for broader applications beyond catalysis, particularly in designing of black titania-based materials.

Industrial Grade Resin as Reusable Catalyst for Amidoalkylation of γ-Hydroxy Lactams.

Herein, we disclose a selective, versatile, accessible, cost-effective and highly efficient cation-exchange industrial grade INDION 130 resin as a reusable catalyst for the synthesis of 3-substituted isoindolinones from various γ-hydroxy lactams and a variety of C, N, O, and S nucleophiles involving N-acyliminium ion intermediates under mild reaction conditions. Mechanistic studies suggested the generation of a different kind of kinetically and thermodynamically controlled intermediates/eliminated products, which further converted to their corresponding products depending upon the nucleophile, reaction parameter and nitrogen substitution (benzyl vs. aryl) of the substrate (succinamidals vs. phthalimidals). The easy synthesis, efficient reactivity and selectivity, broad substrate scope with verities of C, N, O, and S nucleophiles, and efficient recycling make the catalyst and the protocol economical and sustainable.

Mechanistic Insight of Sensing Hydrogen Phosphate in Aqueous Medium by Using Lanthanide(III)-Based Luminescent Probes.

The development of synthetic lanthanide luminescent probes for selective sensing or binding anions in aqueous medium requires an understanding of how these anions interact with synthetic lanthanide probes. Synthetic lanthanide probes designed to differentiate anions in aqueous medium could underpin exciting new sensing tools for biomedical research and drug discovery. In this direction, we present three mononuclear lanthanide-based complexes, EuLCl3 (1), SmLCl3 (2), and TbLCl3 (3), incorporating a hexadentate aminomethylpiperidine-based nitrogen-rich heterocyclic ligand L for sensing anion and establishing mechanistic insight on their binding activities in aqueous medium. All these complexes are meticulously studied for their preferential selectivities towards different anions such as HPO42-, SO42-, CH3COO-, I-, Br-, Cl-, F-, NO3-, CO32-/HCO3-, and HSO4- at pH 7.4 in aqueous HEPES (2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid) buffer. Among the anions scanned, HPO42- showed an excellent luminescence change with all three complexes. Job's plot and ESI-MS support the 1:2 association between the receptors and HPO42-. Systematic spectrophotometric titrations of 1-3 against HPO42- demonstrates that the emission intensities of 1 and 2 were enhanced slightly upon the addition of HPO42- in the range 0.01-1 equiv and 0.01-2 equiv., respectively. Among the three complexes, complex 3 showed a steady quenching of luminescence throughout the titration of hydrogen phosphate. The lower and higher detection limits of HPO42- by complexes 1 and 2 were determined as 0.1-4 mM and 0.4-3.2 mM, respectively, while complex 3 covered 0.2-100 µM. This concludes that all complexes demonstrated a high degree of sensitivity and selectivity towards HPO42-.

Catalytic Conversion of Carbon Dioxide Using Binuclear Double-Stranded Helicates: Cyclic Carbonate from Epoxides and Diol.

The construction of sophisticated molecular architectures from chemical subunits requires careful selection of the spacers, precise synthetic strategies, and substantial efforts. Here, we report a series of binuclear double-stranded helicates synthesized from different combinations of pyridyl hydrazone-based multidentate ligands (H2 1, H2 2, H2 3) by increasing the methylene spacer and transition metals (Co, Ni, and Zn). The ligands H2 1 (N'1,N'3-bis((E)-pyridin-2-ylmethylene)malonohydrazide), H2 2 (N'1,N'4-bis((E)-pyridin-2-ylmethylene)succinohydrazide), and H2 3 (N'1,N'5-bis((E)-pyridin-2-ylmethylene)glutarohydrazide) and their respective complexes with Co, Ni, and Zn were obtained. Single-crystal X-ray diffraction studies of these binuclear metallohelicates confirm the double-stranded helical structure of the complexes derived from H2 2. The set of helicates Co-1, Co-2, and Co-3; Ni-1, Ni-2, and Ni-3; and Zn-1, Zn-2, and Zn-3 were investigated for its catalytic activity in the cyclic carbonate formation reaction. Intriguingly, among the synthesized catalyst, Co-1 was found to be better in terms of conversions with the calculated TOF (turnover frequency) of 128/h. The catalytic performance was significantly improved by adding 0.2 mmol of tetrabutylammonium bromide by achieving 76% conversion in 30 min, with the observed TOF of 15,934 h-1/molecule and 7967 h-1/Co center. The results obtained herein show that the double-stranded helicates are effective catalysts for converting both terminal and non-terminal epoxides into their corresponding cyclic carbonates. The striking feature of this catalytic protocol lies in demonstrating the catalytic activity for the conversion of diol to cyclic carbonate, and the detailed kinetic experiments tempted us to propose a tentative reaction mechanism for this conversion.

Binuclear Double-Stranded Helicates and Their Catalytic Applications in Desymmetrization of Mesodiols.

The ligand L1 of 4-methyl-2,6-diformylphenol and L2 of 4- tert-butyl-2,6-diformylphenol are synthesized through Schiff base condensation with rac-, ( R)-(+), or ( S)-(-)-1,1'-binaphthyl-2,2'-diamine (BNDA). As a result, the racemic L1rac, L2rac, and enantiopure L1RR, L1SS, L2RR, and L2SS ligands are obtained incorporating Cu(II) and Zn(II) salts by a simple one-pot metal template method. The series of dinuclear complexes of [M2LX2] (here, M = Cu2+, Zn2+; X = acetate ion, chloride ion; L = L1RR, L1SS, L1rac, L2RR, L2SS, L2rac) formulas are obtained in common. Among them, the single crystal X-ray structures for [Zn2L1rac(OAc)2] and [Zn2L1SSCl2] complexes are obtained. The detailed crystal structure and the chiroptical studies performed on these complexes dictates a self-sorting behavior in their self-assembly process and illustrate a chirality transfer from the ligand to the metal center on the complexes. The enantiopure dinuclear complexes [M2LRRX2] and [M2LSSX2] generate enantiopure ΛΛ and ΔΔ isomers, respectively, but the racemic complexes produce only homochiral ΛΛ and ΔΔ assemblies. The detailed studies based on UFLC (Ultra Fast Liquid Chromatography), CD, and single crystal X-ray structure together show the absence of heterochiral ΛΔ mesocate. All these complexes are adapted as catalysts for desymmetrization of various mesodiols, and the enantiopure complexes are found to give efficient enantioselectivity in desymmetrization of mesodiols with benzoyl chloride to monobenzoylated ester providing 98% yield and 92% ee.

Enantiomeric Resolution of Asymmetric-Carbon-Free Binuclear Double-Stranded Cobalt(III) Helicates and Their Application as Catalysts in Asymmetric Reactions.

A series of double-stranded binuclear helicates [Co2(H1)2]4+, [Co2(H2)2]4+, and [Co2(H3)2]4+, derived from monodeprotonated bis-pyridyl hydrazine-based ligands of H21, H22, and H23 with one, two, and three -CH2 spacers, were obtained. These asymmetric-carbon-free racemic helicates were separated into their ΔΔ and ΛΛ enantiomers. The resolved helicates were examined for the first time as enantioselective catalysts in asymmetric benzoylation and nitroaldol reactions.

Coordinatively Unsaturated Lanthanide(III) Helicates: Luminescence Sensors for Adenosine Monophosphate in Aqueous Media.

Coordinatively unsaturated double-stranded helicates [(H2 L)2 Eu2 (NO3 )2 (H2 O)4 ](NO3 )4 , [(H2 L)2 Tb2 (H2 O)6 ](NO3 )6 , and [(H2 L)2 Tb2 (H2 O)6 ]Cl6 (H2 L=butanedioicacid-1,4-bis[2-(2-pyridinylmethylene)hydrazide]) are easily obtained by self-assembly from the ligand and the corresponding lanthanide(III) salts. The complexes are characterized by X-ray crystallography showing the helical arrangement of the ligands. Co-ligands at the metal ions can be easily substituted by appropriate anions. A specific luminescence response of AMP in presence of ADP, ATP, and other anions is observed. Specificity is assigned to the perfect size match of AMP to bridge the two metal centers and to replace quenching co-ligands in the coordination sphere.

Sensing of phosphates by using luminescent Eu(III) and Tb(III) complexes: application to the microalgal cell Chlorella vulgaris.

Phenanthroline-based chiral ligands L(1) and L(2) as well as the corresponding Eu(III) and Tb(III) complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F(-), Cl(-), Br(-), I(-), NO3(-), NO2(-), HPO4(2-), HSO4(-), CH3COO(-), and HCO3(-). Among the anions, HPO4(2-) exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties.

Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing.

Phenanthroline-based hexadentate ligands L(1) and L(2) bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La(III), Eu(III), Tb(III), Lu(III), and Y(III) metal ions, were synthesized, and the crystal structures of [ML(1)Cl(3)] (M=La(III), Eu(III), Tb(III), Lu(III), or Y(III)) complexes were determined. Solvent or water molecules act as coligands for the rare-earth metals in addition to halide anions. The big Ln(III) ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu(III), Tb(III), Lu(III), and Y(III) centers with smaller ionic radii show CN=9. Complexes of L(2), namely [ML(2)Cl(3)] (M=Eu(III), Tb(III), Lu(III), or Y(III)) ions could also be prepared. Only the complex of Eu(III) showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine-5'-triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine-5'-diphosphate (ADP) and adenosine-5'-monophosphate (AMP) was found. (31)P NMR spectroscopic studies revealed the formation of a [EuL(2)(ATP)] coordination species.