A Cubane-Like Cobalt Complex in Water Oxidation: Synthesis, True Catalyst, and Catalytic Mechanism.

In this study, we examine the OER performance of a known cuboidal Co complex, ([Co(dpy{OH}O)(OAc)(HO)](ClO)(1.7HO) dpk = di(2-pyridyl) ketone, (complex 1)). Our experiments show that at a pH of 11, complex 1 acts as a precursor for the true oxygen-evolution reaction (OER) catalyst.

Controlling pseudopolymorphism robust and repetitive solvent-containing supramolecular interactions in urea-based isostructural coordination polymers.

In a systematic study, six pseudopolymorphic coordination polymers containing the ditopic 1,3-di(pyridin-4-yl)urea ligand (4bpu) constructed with d metal cations, possessing the formula {[M(4bpu)I]S} [(M = Zn, Cd and Hg), (S = MeOH or EtOH)], namely Zn-MeOH, Zn-EtOH, Cd-MeOH, Cd-EtOH, Hg- and Hg-EtOH were obtained. The title compounds were characterized by single-crystal X-ray diffraction analysis (SC-XRD), elemental analysis (CHN), FT-IR spectroscopy, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). The diffraction studies show that these compounds are isostructural 1D zig-zag chain coordination polymers which is also confirmed using XPac 2.

Synthesis and characterization of metal dithiocarbamate derivatives of (S)-1-phenyl-1,2,3,4-tetrahydroisoquinoline.

Five metal dithiocarbamate complexes [M(PTHIQDTC)] [where PTHIQDTC is (S)-1-phenyl-1,2,3,4-tetrahydroisoquinoline dithiocarbamate anion and M is Ni(II) (1), Sn(II) (2), Hg(II) (3), Pb(II) (4) and Zn(II) (5)] were synthesized from the reaction of MX (X is Cl for 1-3 and OAc for 4-5) with ligand of triethylammonium (S)-1-phenyl-1,2,3,4-tetrahydroisoquinoline dithiocarbamate [EtNH][PTHIQDTC] in methanolic solution at room temperature. The five complexes were characterized by IR, H andC NMR, mass spectrometry, elemental analysis and TGA analysis. Recrystallization of [Zn(PTHIQDTC)] (5) in dimethylsulfoxide (DMSO) converts 5 to [Zn(PTHIQDTC)(DMSO)] (6).

Synthesis of pyrrole-fused dibenzoxazepine/dibenzothiazepine/triazolobenzodiazepine derivatives via isocyanide-based multicomponent reactions.

An efficient and facile synthesis of pyrrole-fused dibenzoxazepine/dibenzothiazepine/triazolobenzodiazepine derivatives was developed through the isocyanide-based multicomponent reaction of isocyanides, -diactivated olefins, and cyclic imines such as dibenzoxazepine, dibenzothiazepine, and triazolobenzodiazepine under solvent- and catalyst-free conditions. Purposefully, this approach produced various bioactive scaffolds using environmentally friendly, mild, and simple conditions. Due to their bioactive moieties, these compounds with exclusive fluorescence properties may attract great attention in biomedical applications, clinical diagnostics, and conjugate materials.

Solvent and additive-controlled supramolecular isomerism in zinc coordination polymers.

A new series of Zn(II) supramolecular isomers containing ditopic 1,3-di(pyridin-4-yl)urea (4bpu) ligand were synthesized and characterized by infrared analysis, elemental analysis and TGA as well as single-crystal X-ray diffraction analysis. Four solvent-induced pseudopolymorphic zinc (II) coordination polymers (CPs), namely, {[Zn(4bpu)(OAc)](CHOH)} (1), {[Zn(4bpu)(OAc)](CHOH)} (2), {[Zn(4bpu)(OAc)](HOCHCHOH)} (3), and {[Zn(4bpu)(OAc)](0.5HO)} (4), were prepared by the reaction of Zn(OAc).

Effect of geometric isomerism on the anticancer property of new platinum complexes with glycine derivatives as asymmetric N, O donate ligands against human cancer.

In this project, to fallow the anticancer ability of new Pt drugs, several new Pt complexes were synthesized with the asymmetric bidentate glycine derivatives, as named propyl- and hexyl glycine (L), in the general formula: [Pt(NH)(L)]NO, and cis- and trans-[Pt(L)]. The structure of two cis- and trans-[Pt(propylgly)] complexes was proved by single crystallography analysis. However, all complex structures were characterized by various methods of H NMR, C NMR, Pt NMR, FTIR, LC-Mass, and Raman spectroscopy.

Sulfur- and DABCO-Promoted Reaction between Alkylidene Rhodanines and Isothiocyanates: Access to Aminoalkylidene Rhodanines.

In this work, an efficient sulfur- and DABCO-promoted reaction for the synthesis of aminoalkylidene rhodanines from available alkylidene rhodanines and isothiocyanates is reported. A tandem process including sulfurative annulation/ring-opening by liberation of a CS molecule/olefination allows the synthesis of aminoalkylidene rhodanines with acceptable functional group tolerance. Chemo- and stereoselectivity, operational simplicity, and synthetically useful yields are some highlighted advantages of these transformations.

Structure-bioactivity relationship study on anticancer Pd and Pt complexes with aliphatic glycine derivative ligands.

To investigate the structure and bioactivity relationship, six Pd(II)/Pt(II) complexes with N-isobutylglycine (L) and cyclohexylglycine (L) as N^O amino acid bidentate ligands, 1,10'-phenanthroline (phen) and 2,2'-bipyridine (bipy) as N^N donor ligands, and [Pd(L)(bipy)]NO (1), [Pd(L)(bipy)]NO (2), [Pd(L)(phen)]NO (3), [Pd(L)(phen)]NO·2HO (4), [Pt(L)(phen)]NO (5), along with [Pt(L)(phen)]NO (6) were prepared and then characterized. The geometry of each compound was validated by doing a DFT calculation. Furthermore, tests were conducted on the complexes' water solubilities and lipophilicity.

Three-Component Reaction between 3-Acetylcoumarins, Amines, and Elemental Sulfur: A Designed Approach to 3-Amino-4-thieno[3,2-]coumarins.

In this work, a series of novel 3-amino-4-thieno[3,2-]coumarins were designed and synthesized by a one-pot, catalyst-free, and three-component reaction of 3-acetylcoumarins with amines and elemental sulfur. Readily available starting materials, simple heating conditions, facile installation of a sulfur atom into the molecule using S as a sulfur source, acceptable functional group tolerance, and synthetically useful yields are some highlighted benefits of this process.

Efficient synthesis of novel thiadiazolo[2,3-b]quinazolin-6-ones catalyzed by diphenhydramine hydrochloride-CoCl⋅6HO deep eutectic solvent.

In this research, a new Lewis acid-based deep eutectic solvent (LA-DES) was synthesized using diphenhydramine hydrochloride and CoCl·6HO, (2[HDPH]:CoCl), and identified by FT-IR and HNMR techniques. The physicochemical properties of this LA-DES, such as thermal behavior, thermal stability, and solubility in common solvents were also investigated. The catalytic ability of 2[HDPH]:CoCl was ascertained in the efficient synthesis of a novel array of thiadiazolo[2,3-b]quinazolin-6-one scaffolds via a one-pot three-component reaction of dimedone/1,3-cyclohexanedione, aldehydes, and 5-aryl-1,3,4-thiadiazol-2-amines/3-(5-amino-1,3,4-thiadiazol-2-yl)-2H-chromen-2-one under solvent-free conditions.

In Situ Conversion of Ligand to a Coordination Polymer via a Core@Shell Crystal: A Multi-Step Phase-Dependent Structural Transformation.

Two pseudopolymorphic 1D coordination polymers of the formulas [Cd(3,3'-pytz)(CHOH)(ClO)] () and [Cd(3,3'-pytz)(CHCN)(ClO)] () have been prepared using the electron-deficient 3,6-bis(pyridin-3-yl)-1,2,4,5-tetrazine (3,3'-pytz) ligand and cadmium perchlorate in the chloroform/methanol and chloroform/acetonitrile solvent system, respectively. It was observed that compounds and experienced one-step (CP → CP) single-crystal-to-powder structural transformation to the pure water-coordinated compound [Cd(3,3'-pytz)(HO)(ClO)] () by absorbing water vapor from air (solid-gas phase transformation). Interestingly, compounds , , and undergo a different transformation path and show an in situ unique three-step (CP → CP → Ligand → CP) single-crystal-to-single-crystal (SCSC) structural transformation process through soaking in deionized water (solid-liquid phase transformation).

Using Triazolobenzodiazepine as the Cyclic Imine in Various Types of Joullié-Ugi Reactions.

The triazolobenzodiazepine as a cyclic imine was employed in a variety of Joullié-Ugi reactions, and three new families of unique triazolobenzodiazepine connected to carboxamide and tetrazole products were synthesized via a three-component reaction of the cyclic imine and isocyanides with each species of a carboxylic acid/water/TMSN under mild conditions in high yields. Furthermore, triazolobenzodiazepine imine was used in an interesting strategy based on the modified Ugi reaction (pseudo-Joullié-Ugi reaction) of cyclic imines with an isocyanide and acetylenedicarboxylates under catalyst-free conditions for the synthesis of triazolobenzodiazepine-fused pyrroles. Mechanistic investigation reveals that triazolobenzodiazepine-fused pyrroles have been generated via a surprising route.

Diphenhydramine Hydrochloride-CuCl as a New Catalyst for the Synthesis of Tetrahydrocinnolin-5(1)-ones.

The current study deals with the synthesis and characterization of a novel catalyst made from diphenhydramine hydrochloride and CuCl ([HDPH]Cl-CuCl). The prepared catalyst was thoroughly characterized using various techniques, such as H NMR, Fourier transform-infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis and derivative thermogravimetry. More importantly, the observed hydrogen bond between the components was proven experimentally.

The new synthesis of pyrrole-fused dibenzo[,][1,4]oxazepine/thiazepines by the pseudo-Joullié-Ugi reaction an unexpected route with high chemoselectivity.

A novel and unexpected route for synthesizing pyrrole-fused dibenzoxazepines/thiazepines has been designed based on a modified Ugi reaction of cyclic imines with isocyanides and acetylenedicarboxylates under catalyst-free conditions. Mechanism investigation indicates that this process is carried out through the production of zwitterion species (Huisgen's 1,4-dipole), which is a key intermediate in the chemoselectivity of products. This Huisgen's 1,4-dipole is trapped with isocyanides and a variety of pyrrole-fused dibenzoxazepines/thiazepines are synthesized in a simple one-pot operation with high yields and chemoselectivity.

Substrate-Controlled Diastereo- and Enantiodivergent Synthesis of Bis-Spirocyclopropyloxindoles from Available Isatin as a Single Starting Material.

The first diastereo- and enantiodivergent asymmetric synthesis of new bis-spirocyclopropyloxindole scaffolds has been accomplished from the readily available isatin as a single starting material. Four -(1,2,3), -(1,2,3), rel-(1,2,3), and -(1,2,3) configurations of desired products were constructed in excellent enantiopurity via a simple switch in substrates using the chiral auxiliary-controlled method. The absolute configuration of cycloadducts with three contiguous quaternary/tertiary stereogenic centers was confirmed through X-ray diffraction analysis.

Water Content-Controlled Formation and Transformation of Concomitant Pseudopolymorph Coordination Polymers.

Two concomitant pseudopolymorph coordination polymers {[CdL(OAc)]·2DMSO} () and {[CdL(OAc)]·2.75HO} () were synthesized by self-assembly of 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene () and cadmium acetate in DMSO. Single-crystal X-ray diffraction confirmed that 1D ladder structural motifs exist for pseudopolymorphs and which contain DMSO and water guest molecules, respectively.

Biocatalytic stereoselective synthesis of pyrrolidine-2,3-diones containing all-carbon quaternary stereocenters.

Highly functionalized pyrrolidine-2,3-diones can be synthesized efficiently and stereoselectively under mild conditions using a biocatalytic approach. The reaction led to the formation of new all-carbon quaternary stereocenters from laccase (Novozym 51003) catalyzed oxidation of catechols to -quinones and subsequent 1,4-addition with 3-hydroxy-1,5-dihydro-2-pyrrol-2-ones. The reaction was conducted with various substituents on both reactants, resulting in 13 products in moderate to good yields (42-91%).

Regioselective synthesis of enantiopure 1,2- and 1,3-dispirooxindoles along with a DFT study.

In the present study, a library of important enantiopure dispirooxindole [indolizidine, pyrrolizidine, and pyrrolidine] derivatives with three or four contiguous and two quaternary stereogenic centers using different amino acids (pipecolic acid, sarcosine, proline and hydroxyproline) were synthesized in high yields (up to 96%) through a regio- and diastereoselective (up to 99 : 1) multicomponent 1,3-dipolar cycloaddition strategy. Based on the results, the alteration of amino acids led to a change in the regioselectivity and unusual regioisomers (pyrrolizidine indolizidine/pyrrolidine) were obtained to construct a novel enantiopure 1,3-dispirooxindole skeleton. The stereochemical outcome of the cycloaddition was determined by single crystal X-ray diffraction analysis and the self-disproportionation of enantiomers (SDE) test confirmed the enantiomeric purity of the desired products.

Biological Activity of Two Anticancer Pt Complexes with a Cyclohexylglycine Ligand against a Colon Cancer Cell Line: Theoretical and Experimental Study.

Because of their extraordinary ability to disrupt the natural structure of nucleic acids, metal complexes could be used in cancer therapy. In this study, cyclohexylglycine () as a ligand and two new Pt complexes, [Pt(NH)(L)]NO () and [Pt(bipy)(L)]NO (), were synthesized and characterized by elemental analysis, LC-MS, UV-vis spectrometry, FT-IR, H NMR spectroscopy, C NMR spectroscopy, Pt NMR spectroscopy, HPLC analysis, and single-crystal X-ray diffraction. Complex crystallized in the orthorhombic space group, and density functional theory (DFT) was used to describe its structural parameters were described in detail.

Synthesis of triarylpyridines with sulfonate and sulfonamide moieties via a cooperative vinylogous anomeric-based oxidation.

Herein, novel magnetic nanoparticles with pyridinium bridges namely FeO@SiO@PCLH-TFA through a multi-step pathway were designed and synthesized. The desired catalyst and its corresponding precursors were characterized with different techniques such as Fourier transform infrared (FT-IR) spectroscopy, H NMR, C NMR, Mass spectroscopy, energy dispersive X-ray (EDX) analysis, thermogravimetric/derivative thermogravimetry (TG/DTG) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM). In addition, the catalytic application of the prepared catalyst in the synthesis of new series of triarylpyridines bearing sulfonate and sulfonamide moieties via a cooperative vinylogous anomeric-based oxidation was highlighted.

Humidity-Induced Structural Transformation in Pseudopolymorph Coordination Polymers.

Three cadmium coordination polymers, namely, {[CdL(OAc)](CHOH)} (), {[CdL(OAc)](CHCN)} (), and [CdL(OAc)(HO)] (), were synthesized by an exoditopic 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene Schiff base ligand () and cadmium acetate in the presence of different solvent systems. Single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis showed that 1D ladder pseudopolymorphic compounds ( and ) transformed to the solvent-free 1D linear compound through a rare case of water absorption from air at room temperature. Interestingly, compound was transformed to compound through a dissolution-recrystallization structural transformation process.

Chemoselective synthesis of fully substituted pyrroles a one-pot four-component isocyanide-based reaction.

Small-ring heterocycles comprising pyrrole and pyrazole are well known for their rich biological properties. In this article, an efficient green sonochemical approach was designed for the synthesis of novel, fully substituted pyrroles connected to pyrazole scaffolds via a one-pot, four-component isocyanide-based sequential reaction. This reaction was carried out using various 5-amino-pyrazoles, aldehydes, dialkyl acetylenedicarboxylates and isocyanides for the synthesis of fully functionalized pyrroles with high chemoselectivity in the presence of a catalytic amount of PTSA·H2O, in good to excellent yields under ultrasound irradiation.

Iodide-Catalyzed Selenium-Assisted Sequential Multicomponent Synthesis of a Luminescence Benzo-Oxazino-Isoindole Framework.

We have described an unexpected pathway using the R-NC/Se system for the synthesis of the unreported benzo-oxazino-isoindole framework by the iodide-catalyzed selenium-assisted sequential multicomponent reaction of the Knoevenagel adduct of ninhydrin and malononitrile, isocyanide, amine, and elemental selenium under mild reaction conditions. The photophysical properties of the products were investigated by absorption and emission spectroscopy, revealing that the new heterocyclic system has good fluorescence properties.

Magnetic chitosan nanocomposite: As a novel catalyst for the synthesis of new derivatives of N-sulfonylamidine and N-sulfonylimidate.

This study reports the synthesis and characterization of a highly active catalyst based on chelated copper iodide on magnetic chitosan-salicylaldehyde Schiff base. This catalyst was successfully used for the three-component reaction of N-propargylphthalimide, tosylazide, and NH or OH containing nucleophiles to access new classes of N-sulfonylamidine or N-sulfonylimidate derivatives. The products, which were constructed via an in situ generated sulfonyl keteneimine intermediate, were obtained in good to excellent yields.

Low-Turn-On-Voltage, High-Brightness, and Deep-Red Light-Emitting Electrochemical Cell Based on a New Blend of [Ru(bpy)] and Zn-Diphenylcarbazone.

Deep red light-emitting electrochemical cells were prepared based on a blend of [Ru(bpy)], a cationic complex, and a neutral Zn(II)-complex based on diphenylcarbazone ligands, named Zn(DPCO). The crystal structure of the Zn(DPCO) (bpy)] molecule revealed that the DPCO ligand has been deprotonated to form DPCO and coordinated to the Zn center metal through the C=O and N=N moieties of DPCO. From the cyclic voltammetry results and controlled potential coulometry data of the diphenylcarbazide (DPC) ligand, it is possible to establish that DPC is oxidized in an irreversible process at +0.