Micellar catalysis: Polymer bound palladium catalyst for carbon-carbon coupling reactions in water.

Metallosurfactants, defined here as hydrophobic metal-containing groups embedded in hydrophilic units when dispersed in water, emanate in the formation of metallomicelles. This approach continues to attract great interest for its ability to serve as micellar catalysts for various metal-mediated chemical transformations in water. Indeed, relevant to green chemistry, micellar catalysis plays a preeminent function as a replacement for organic solvents in a variety of chemical reactions. There are several methods for the interaction of metal complexes (catalysts or catalyst precursors) and surfactants for producing micellar aggregates. A very effective manner for achieving this involves the direct bonding of the metal center to the amphiphilic polymeric materials. Herein, we describe the synthesis of a metallosurfactant containing a palladium complex covalently incorporated into a CO2-based triblock polycarbonate derived using a dicarboxylic acid chain-transfer agent. This amphiphilic polycarbonate was shown to self-assemble in water to provide uniform and spherical micelles, where the catalytic metal center is located in the hydrophobic portion of the micelle. The resulting metallosurfactant was demonstrated to effectively catalyze carbon-carbon coupling reactions at very low catalyst loadings.

Physicochemical and Anti-fungal Studies of the Pharmaceutical Co-crystal/Salt of Fluconazole.

Crystal engineering is one green alternative to organic synthesis that can be used to manipulate molecular behavior promptly and economically. We report the preparation and characterization of the pharmaceutical organic salt (FLC-C) of fluconazole (FLC) and organosulfonate (NDSA-2H), based on the sulfonate-pyridinium supramolecular synthon. Structural studies validate the crystallization of the two-component stoichiometric crystal with two molecules of water in the triclinic P1̅ space group. The anticipated proton transfer between the crystal forms leads to ionic interactions, augmenting the organic salt's thermal stability. Hirshfeld studies of FLC-C help to understand the role and significance of different types of intermolecular interactions responsible for crystal packing. The structural and theoretical studies indicate the absence of π-π interactions in FLC-C, which account for the incipience of solid-state emission in the product. The solubility studies establish augmented aqueous solubility of FLC-C over pristine FLC at physiological pH values of 2 and 7. Interestingly, in in vitro studies, FLC-C appears to serve as a potential alternative to FLC, displaying a wide spectrum of antifungal activity. FLC-C is active against several human pathogenic yeast strains, including the leading and emerging Candida strains (Candida albicans and Candida auris, respectively), at comparable and/or lower drug concentrations without showing any enhanced host cell toxicity. Interestingly, the pharmaceutical co-crystal also displays fluorescence properties inside the Candida cells.

Syntheses, Structural Characterization, and Cytotoxicity Assessment of Novel Mn(II) and Zn(II) Complexes of Aroyl-Hydrazone Schiff Base Ligand.

This work describes the syntheses, structural characterization, and biological profile of Mn(II)- and Zn(II)-based complexes 1 and 2 derived from the aroyl-hydrazone Schiff base ligand (L1). The synthesized compounds were thoroughly characterized by elemental analysis, Fourier transform infrared spectroscopy (FTIR), UV-vis, electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), and single-crystal X-ray diffraction (s-XRD). Density functional theory (DFT) studies of complexes 1 and 2 were performed to ascertain the structural and electronic properties. Hirshfeld surface analysis was used to investigate different intermolecular interactions that define the stability of crystal lattice structures. To ascertain the therapeutic potential of complexes 1 and 2, in vitro interaction studies were carried out with ct-DNA and bovine serum albumin (BSA) using analytical and multispectroscopic techniques, and the results showed more avid binding of complex 2 than complex 1 and L1. The antioxidant potential of complexes 1 and 2 was examined against the 2,2-diphenyl picrylhydrazyl (DPPH) free radical, which revealed better antioxidant ability of the Mn(II) complex. Moreover, the antibacterial activity of synthesized complexes 1 and 2 was tested against Gram-positive and Gram-negative bacteria in which complex 2 demonstrated more effective bactericidal activity than L1 and complex 1 toward Gram-positive bacteria. Furthermore, the in vitro cytotoxicity assessment of L1 and complexes 1 and 2 was carried out against MDA-MB-231 (triple negative breast cancer) and A549 (lung) cancer cell lines. The cytotoxic results revealed that the polymeric Zn(II) complex exhibited better and selective cytotoxicity against the A549 cancer cell line as was evidenced by its low IC50 value.

Selective formation of discrete versus polymeric copper organophosphates: DNA cleavage and cytotoxic activity.

Copper phosphate metalloligands [Cu(X-dipp)(Pyterpy)]2 [X = H (1), Br (2)], exemplifying expanded 4,4'-bipyridine type molecules, have been synthesized by reacting 4'-(4-pyridyl)-2,2':6',2''-terpyridine (Pyterpy) and para substituted 2,6-diisopropylphenyl phosphate (X-dippH2) with copper acetate. The pendant N,N-ends of dimeric copper phosphates 1 and 2 have been forced to engage in further coordination by limiting the concentration of Pyterpy in the reaction mixture to yield rare Pyterpy bridged corner-shared polymeric copper phosphates [Cu2(X-dippH)(X-dipp)(Pyterpy)(H2O)]n [X = Cl (3), Br (4), I (5)]. The formation of 1-5 is supported by spectroscopic and analytical data. The solid state structures of these compounds have further been confirmed by single-crystal X-ray diffraction studies. Soluble dimeric complexes 1 and 2 have been assessed for their in vitro anti-tumour properties against human breast and colorectal cancer cell lines. The DNA cleavage, protein cleaving and cytotoxicity assays revealed that these compounds are effective in cleaving DNA, while the activity of 1 as an anti-tumor agent is better than 2.

Elusive Double-Eight-Ring Zeolitic Secondary Building Unit.

The double-eight-ring (D8R), an elusive secondary building unit of zeolites, has been stabilized for the first time, both in solution and solid-state. The present study further establishes that any of the three double-ring building blocks of zeolites, viz. D4R, D6R and D8R ([ArPO3Zn(L)]n (n = 4, 6 or 8)), can be preferentially isolated (over the other two) through a careful choice of metal source, aryl phosphate and ancillary ligand, apart from maintaining a meticulous control on the reaction conditions.

Dimensionality Alteration and Intra- versus Inter-SBU Void Encapsulation in Zinc Phosphate Frameworks.

4,4'-Bipyridine-N-oxide (BIPYMO, 1), a less commonly employed coordination polymer linker, has been used as a ditopic spacer to bridge double-four-ring (D4R) zinc phosphate clusters to form novel framework coordination polymers. Zinc phosphate framework compounds [Zn4(X-dipp)4(BIPYMO)2]n·2MeOH [X = H (2), Cl (3), Br (4), I (5); dipp = 2,6-diisopropylphenyl phosphate] have been obtained by treating a methanol solution of zinc acetate with X-dippH2 and BIPYMO (in a 1:1:1 molar ratio) at ambient conditions. Framework phosphates 2-5 can also be obtained by treating the preformed D4R cubanes [Zn(X-dipp)(DMSO)]4 with required quantities of BIPYMO in methanol. Single-crystal X-ray diffraction studies reveal that these framework solids are two-dimensional (2D) networks as opposed to the diamondoid networks obtained when the parent unoxidized 4,4'-bipyridine is used as the linker (Inorg. Chem. 2014, 53, 8959). The two types of voids (viz., smaller intra-D4R and larger inter-D4R) present in these framework solids can be utilized for different types of encapsulation processes. For example, the in situ generated 2D framework 2 encapsulates fluoride ions accompanied by a change in the dimensionality of the framework to yield {[(nC4H9)4N][F@(Zn4(dipp)4(BIPYMO)2)]}n (6). The three-dimensional framework 6 represents the first structurally characterized example of a fluoride-ion-encapsulated polymeric coordination compound or a metal-organic framework. The possibility of utilizing inter-D4R voids as hosts for small organic molecules has been explored by treating in situ generated 2 with a series of organic molecules of appropriate size. Framework 2 has been found to be a selective host for benzil and not for other structurally similar molecules such as benzoquinone, benzidine, anthracene, naphthalene, α-pyridoin, etc. The benzil-occluded isolated framework [benzil@{Zn4(dipp)4(BIPYMO)2}]n (7) has been isolated as single crystals, and its crystal structure determination revealed the binding of benzil molecules to the framework through strong π-π interactions.

Octanuclear zinc phosphates with hitherto unknown cluster architectures: ancillary ligand and solvent assisted structural transformations thereof.

Structural variations in zinc phosphate cluster chemistry have been achieved through a careful selection of phosphate ligand, ancillary ligand, and solvent medium. The use of 4-haloaryl phosphates (X-dippH2) as phosphate source in conjunction with 2-hydroxypyridine (hpy) ancillary ligand in acetonitrile solvent resulted in the isolation of the first examples of octameric zinc phosphates [Zn8(X-dipp)8(hpy)4(CH3CN)2(H2O)2]·4H2O (X = Cl 2, Br 3) and not the expected tetranuclear D4R cubane clusters. Use of 2,3-dihydroxypyridine (dhpy) as ancillary ligand, under otherwise similar reaction conditions with the same set of phosphate ligands and solvent, resulted in isolation of another type of octanuclear zinc phosphate clusters {[(Zn8(X-dipp)4(X-dippH)4(dhpyH)4(dhpyH2)2(H2O)2]·2solvent} (X = Cl, solvent = MeCN 4; Br, solvent = H2O 5), as the only isolated products. X-ray crystal diffraction studies reveal that 2 and 3 are octanuclear clusters that are essentially formed by edge fusion of two D4R zinc phosphates. Although 4 and 5 are also octanuclear clusters, they exhibit a completely different cluster architecture and have been presumably formed by the ability of 2,3-dihydroxypyridine to bridge zinc centers in addition to the X-dipp ligands. Dissolution of both types of octanuclear clusters in DMSO followed by crystallization yields D4R cubanes [Zn(X-dipp)(DMSO)]4 (X = Cl 6, Br 7), in which the ancillary ligands such as hpy, H2O, and CH3CN originally present on the zinc centers of 2-5 have been replaced by DMSO. DFT calculations carried out to understand the preference of Zn8 versus Zn4 clusters in different solvent media reveal that use of CH3CN as solvent favors the formation of fused cubanes of the type 2 and 3, whereas use of DMSO as the solvent medium promotes the formation of D4R structures of the type 6 and 7. The calculations also reveal that the vacant exocluster coordination sites on the zinc centers at the bridgehead positions prefer coordination by water to hpy or CH3CN. Interestingly, the initially inaccessible D4R cubanes [Zn(X-dipp)(hpy)]4·2MeCN (X = Cl 8, Br 9) could be isolated as the sole products from the corresponding DMSO-decorated cubanes 6 and 7 by combining them with hpy in CH3CN.

Is single-4-ring the most basic but elusive secondary building unit that transforms to larger structures in zinc phosphate chemistry?

Haloaryl phosphates (X-dippH2, X = Cl, Br, I) react with zinc acetate in the presence of collidine or 2-aminopyridine (2-apy) to yield zinc phosphate clusters [Zn(X-dipp)(collidine)]4 (X = Cl (1), Br (2), I (3)) and [Zn(X-dipp)(2-apy)]4·2MeOH (X = Cl (4), Br (5), I (6)), respectively. Single-crystal X-ray diffraction studies reveal that collidine and 2-apy capped zinc phosphates 1-6 exist as discrete tetrameric zinc phosphate molecules, exhibiting a cubane-shaped D4R core. In contrast, when the same reaction has been carried out in the presence of 4-cyanopyridine (4-CNpy), polymeric zinc phosphates {[Zn4(X-dipp)4(4-CNpy)2(MeOH)2]·2H2O}n (X = Cl (7), Br (8), I (9)) have been isolated. Compounds 7-9 are square-wave-shaped, one-dimensional polymers composed of fused S4R repeating units. The common structural motif found both in D4R cubanes 1-6 and polymers 7-9 is the S4R building block, which presumably undergoes further fusion because of the coordinative unsaturation at zinc and the simultaneous presence of free P═O. The closed shell cubanes 1-6 are obviously formed by a face-to-face dimerization involving two S4R units in which the two P═O groups are in cis-configuration. On the other hand, the one-dimensional (1-D) square-wave polymers 7-9 are formed from a face-to-face association of S4R building units in which the two P═O groups are in a trans-configuration. In order to stabilize these elusive S4R zinc phosphates, the reaction between Cl-dippH2 and zinc acetate was carried out in the presence of excess imidazole as an ancillary ligand (1:1:4), although only an imidazole decorated cubane cluster [Zn(Cl-dipp)(imz)]4.2MeOH (10) was isolated. The chelating N,N'-donor 1,10-phenanthroline ligand was used to eventually isolate cyclic S4R phosphate [Zn(µ2-Cl-dipp)(1,10-phen)(OH2)]2·MeOH·H2O (11). The change of Zn(2+) source to zinc nitrate and the phosphate source to 2,6-dimethylphenyl phosphate (dmppH2) led to the isolation of another polymeric phosphate [Zn(dmpp)(MeOH)]n (12), with a zigzag backbone, formed through an edge-to-edge to polymerization of S4R building units with P═O groups in trans-configuration. The isolation of four different structural types of zinc phosphates A-D in the present study can be rationalized in terms of fusion of S4R rings in a variety of ways to either produce discrete clusters or 1-D polymers.

Discrete {Gd(III)4M} (M = Gd(III) or Co(II)) pentanuclear complexes: a new class of metal-organophosphate molecular coolers.

The first examples of homo- and hetero-polymetallic organophosphates of gadolinium are reported. Magnetic measurements reveal a higher magnetic entropy change for the isotropic {Gd(III)5} complex (25.8 J kg(-1) K(-1)) as compared to the heterometallic {Gd(III)4Co(II)} complex (20.3 J kg(-1) K(-1)), which is attributable to a change in magnetic coupling as estimated from DFT calculations.

Mixed micellization and interfacial properties of dodecyltrimethylammonium bromide and tetraethyleneglycol mono-n-dodecyl ether in absence and presence of sodium propionate.

Mixed micelle formation and interfacial properties of aqueous binary surfactant combinations of dodecyltrimethylammonium bromide (C12TAB) and tetraethyleneglycol mono-n-dodecyl ether (C12E4) at 30 degrees C in absence and presence of sodium propionate (NaPr) have been investigated. The critical micelle concentration, aggregation number, micropolarity and interfacial adsorption have been quantitatively estimated by surface tension and steady-state fluorescence measurements. The micellar and adsorption characteristics like composition, activity coefficients and mutual interaction parameters have been estimated following different theoretical treatments like that of Clint, Rubingh, Rodenas, Maeda, Blankschtein and Rosen. The analysis reveals very small mole fraction of cationic surfactant in both the mixed micelles and mixed monolayer inspite of synergism. Blankschtein's model predicts a continuous decrease in synergism due to the salt effect of NaPr; Rubingh's approach, on the contrary, indicates an increase in it above 30 mM of NaPr concentration. Aggregation number variation with NaPr indicates the same. Mixed monolayer shows better synergism compared to that in mixed micelles which increases with the addition of sodium propionate above 30 mM concentration.