Synthesis, spectroscopic findings and crystal engineering of Pb(ii)-Salen coordination polymers, and supramolecular architectures engineered by σ-hole/spodium/tetrel bonds: a combined experimental and theoretical investigation.

Spontaneous self-assembly is one of the available synthetic routes to achieve structurally versatile and unique crystal complexes with selected metal-ligand combinations in the spirit of pseudohalides. In this endeavour, we designed a novel 1D coordination polymer (CP), [(Cd)(Pb)(L)(η1-NCS)(η1-SCN)] n (1), using a compartmental Salen ligand (H3L) in the presence of NaSCN. The characterization of the CP was accomplished using several spectroscopic techniques: MALDI-TOF, PXRD, SEM, EDX mapping, and single-crystal X-ray crystallography. The CP crystallizes in the monoclinic space group P21/c with Z = 4. SCXRD reveals Cd(ii) and Pb(ii) metal ions fulfilled distorted square pyramidal and hemi-directed coordination spheres. Cd(ii) is placed in the inner N2O2 and heavier Pb(ii) in the outer O4 compartments of the de-protonated form of the ligand [L]2-. Supramolecular interactions in the intricate crystal structure produced attractive molecular architectures of the compound. The flexible aliphatic -OH pendent group coordinates with the Pb(ii) ions. This unique binding further elevates the supramolecular crystal topographies. The supramolecular interactions were authenticated by Hirshfeld surface analysis (HSA). The observation of the recurring unconventional tetrel bonds was rationalized by DFT calculations and surface plots of molecular electrostatic potential (MEP). In the 1D polymeric chain in the complex, the O-atom of the -OH groups shows a tetrel bonding interaction with the Pb atom. We have found that the combination of QTAIM/NCI and QTAIM/ELF plots helps reveal the nature of these contacts. Moreover, the QTAIM/ELF plot determines the donor-acceptor interaction between the O-atom and the Pb atom, establishing the σ-hole. Agreeably, the σ-hole interaction also helps Pb(ii) serve as a Lewis acid in the complex. Finally, spodium and tetrel bonds are formed, possible thanks to a hemi-directional coordination sphere of the Pb atoms in the polymer described.

Dicyanamide-intertwined assembly of two new Zn complexes based on N2O4-type pro-ligand: Synthesis, crystal networks, spectroscopic insights, and selective nitroaromatic turn-off fluorescence sensing.

Two new dicyanamide bridged multinuclear Zn complexes, [Zn2(L1)(µ1,5-dca)2(µ1-dca)]n (1) and [Zn2(L2)(µ1,5-dca)2(µ1-dca)]n (2) have been synthesized using N2O4-based pro-ligands (H2L1 = N,N'-bis(5-bromo-3-methoxysalicylidenimino)-1,3-diaminopropane, H2L2 = N,N'-bis(3-ethoxysalicylidene)-2,2-dimethyl-1,3-propanediamine) and characterized by microanalytical and spectroscopic techniques. Both complexes are stable in solution and solid-state. Thermogravimetric analysis (TGA) findings showed that complexes are stable at room temperature. Single-crystal X-ray diffraction (SCXRD) has proven that complexes are identical structures where two zinc metal ions are crystallographically independent. The directional properties of dicyanamide co-ligands via µ1,5 bridging have resulted in different connectivity of zinc metal ions leading to 1D templates. SCXRD revealed some notable non-covalent interactions (π⋯π, C-H····π, and H-bonding) in their solid-state crystal structures. 1-2 have strong fluorescence behaviour over pro-ligands, which may be quenched in the presence of various electron-deficient explosive nitroaromatic compounds (epNACs). Complex 2 fluorescence intensity is sharper than 1; hence the former retained high sensitivity and selectivity for trinitrophenol (TNP). The enhancement of fluorescence mechanism, detection limit (LOD), and the quenching constant (KSV) have been calculated using the Stern-Volmer equation (SV), where the KSV value for TNP is found to be 1.542 × 104 M-1. The solution phase quenching mechanism has been rationalized by (a) electrostatic interactions through charge-transfer complex, (b) photo-induced electron transfer (PET) by the HOMO-LUMO energy gap via DFT, and (c) fluorescence resonance energy transfer (FRET). Finally, complex 2 is applied as a sensor by turn-off fluorescence response to detecting TNP nitroaromatics in the DMF medium.

Dextrin-mediated synthesis of Ag NPs for colorimetric assays of Cu(2+) ion and Au NPs for catalytic activity.

A facile one-pot approach for rapid synthesis of silver and gold nanoparticles (Ag NPs and Au NPs) with narrow size distribution and good stability was described by reducing silver nitrate and chloroauric acid with polysaccharide dextrin. Here, dextrin was used as both a reducing and stabilizing agent for synthesis of NPs. The as-synthesized Ag NPs and Au NPs were characterized by UV-visible absorption spectroscopy, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The Ag NPs and Au NPs exhibited an absorption maxima at 404 and 547 nm respectively. TEM images showed NPs in the range of 8-28 nm. The crystallinity of the NPs was measured by XRD analysis. Furthermore, the as-prepared Ag NPs revealed colorimetric sensor property for detection of Cu(2+) ions based on changes in absorbance resulting from metal ion-induced aggregation of NPs or direct deposition of metal ions onto NPs. The as-prepared Au NPs exhibited a notable catalytic activity toward the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4.

Antibacterial activity of Ag-Au alloy NPs and chemical sensor property of Au NPs synthesized by dextran.

Gold and silver-gold alloy nanoparticles with mean diameter of 10nm and narrow size distribution were prepared by reduction of the correspondent metal precursors using aqueous dextran solution which acts as both a reducing and capping agent. The formation of nanoparticles was characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and dynamic light scattering (DLS). The silver and gold nanoparticles exhibited absorption maxima at 425 and 551 nm respectively; while for the bimetallic Ag-Au alloy appeared 520 nm in between them. TEM images showed monodispersed particles in the range of 8-10nm. The crystallinity of the nanoparticles was assured by XRD analysis. DLS data gave particle size distribution. The dextran stabilized Au nanoparticles used as a colorimetric sensor for detection and estimation of pesticide present in water. The dextran stabilized Ag-Au alloy nanoparticles exhibited interesting antimicrobial activity against bacteria at micromolar concentrations.

Synthesis of methylcellulose-silver nanocomposite and investigation of mechanical and antimicrobial properties.

In this paper we reported preparation of methylcellulose-silver nanocomposite films by mixing of aqueous solution of methylcellulose with silver nitrate followed by casting. The silver nanoparticles were generated in methylcellulose matrix through reduction and stabilization by methylcellulose. The surface plasmon band at 412 nm indicated the formation of Ag nanoparticles. The MC-Ag nanocomposite films were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared (FTIR). The X-ray diffraction analysis of synthesized MC-Ag nanocomposite films revealed that metallic silver was present in face centered cubic crystal structure. Average crystallite size of silver nanocrystal was 22.7 nm. The FTIR peaks of as-synthesized MC-Ag nanocomposite fully designated the strong interaction between Ag nanoparticles and MC matrix. Nano-sized silver modified methylcellulose showed enhanced mechanical properties i.e. the introduction of Ag leading to both strengthening and toughening of MC matrix. The methylcellulose-silver nanocomposite films offered excellent antimicrobial activity against various microorganisms.