Mixed-Valence CuI /CuIII Metal-Organic Frameworks with Non-innocent Ligand for Multielectron Transfer.

We report two novel three-dimensional copper-benzoquinoid metal-organic frameworks (MOFs), [Cu4 L3 ]n and [Cu4 L3 ⋅ Cu(iq)3 ]n (LH4 =1,4-dicyano-2,3,5,6-tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal-organic extended solids. The coordination between the mixed-valence metal and redox-non-innocent ligand L, which promotes through-bond charge transfer between Cu metal sites, allows better metal-ligand orbital overlap of the d-π conjugation, leading to strong long-range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly-covalent Cu(III), non-innocent ligand, and pore environments of these bench stable Cu(III)-containing frameworks on multielectron transfer and electrochemical properties.

Investigation on the Promoter-Induced Rapid Non-Aqueous Media Synthesis of SAPO-35 and Methanol-to-Olefin Reaction.

Microporous SAPO-35 molecular sieves (Levyne type) were synthesized in non-aqueous media by using different inorganic promoters (HClO4 -, HF, H3PO4, and NaNO3) to enhance the rate of crystallization, and the as-synthesized materials were characterized by using different methods such as powder X-ray diffraction spectroscopy (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR), Brunauer-Emmett-Teller (BET) analysis, and X-ray photoelectron spectroscopy (XPS). From PXRD patterns, it was found that all the materials have a highly crystalline nature without any other impurities. SEM images reveal rhombohedral particles in all synthesis conditions. The framework structure of the synthesized materials was identified by FT-IR spectroscopy, and it reveals that all materials gave a similar framework structure. From BET and XPS, we have confirmed that the pore size and pore diameters along with the elemental compositions have a minor change. The 27Al, 31P, and 29Si MAS-NMR spectra of all the promoter-based SAPO-35 materials are close to those of the standard SAPO-35 material. All the above characterization studies reveal the formation of SAPO-35 in a short time with promoters. The catalytic application studies of these synthesized materials for a methanol-to-olefin conversion reaction were performed, and the efficiency of these materials was found to be similar to that of standard materials.

Synthesis of new multivalent metal ion functionalized mesoporous silica and studies of their enhanced antimicrobial and cytotoxicity activities.

In the present study, we have reported the synthesis of a transition metal (Me = Ti, V, and Pd) incorporated into MCM-41 mesoporous molecular sieves (Si/Me = 20) synthesized by the sol-gel method. Their physicochemical properties were studied in detail by standard techniques like low angle powder X-ray diffraction (XRD), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDXS), transmission electron microscopy (TEM), N2 adsorption/desorption studies, and thermogravimetric-differential thermal (TG-DTA) analysis and spectral studies like Fourier transform infrared spectroscopic analysis (FT-IR), diffuse reflectance ultraviolet-visible spectroscopic analysis (UV-Visible-DRS), and X-ray photoelectron spectroscopy (XPS). The XRD patterns prove that the material's phase identity is the same irrespective of metal incorporation. SEM displayed the uniform shape and size of the nanoparticles. The presence of elements such as Ti, V, Pd, Si and O in respective materials is revealed using the EDXS analysis. Around 30% weight loss arose upon calcination from room temperature to 800 °C. BET surface area analysis presented that the parent materials have a high surface area (1024 m2 g-1) which was reduced upon metal incorporation. FT-IR analysis exhibited the framework vibrations of the synthesised materials. UV-Visible-DRS analysis indicated the presence of tetrahedrally coordinated transition metal ions. The multivalent-metal-ion-functionalized mesoporous materials showed significant enhancement in potent antimicrobial and anticancer activity. The antimicrobial activity is because of its low lipophilicity, which no longer allows the materials to enter via the lipid membrane. Thus, the new materials neither obstruct the metal-binding sites nor inhibit the growth of microbe enzymes. Further, the results show that the transition metal ion-containing mesoporous materials possessing good anticancer activity arising from their excessive surface area to volume ratio provided appropriate association with a tumour cell due to the direct penetration of mesoporous materials into the cell wall, causing membrane damage and cell death.

Synthesis of a high-surface area V2O5/TiO2-SiO2 catalyst and its application in the visible light photocatalytic degradation of methylene blue.

In the present study, we synthesized several high-surface area V2O5/TiO2-SiO2 catalysts (vanado titanium silicate, VTS). The synthesized materials were characterized by PXRD, FE-SEM/EDAX, TEM, FTIR, UV-Vis, XPS, fluorescence and photocatalytic activity studies. The small-angle powder X-ray diffraction pattern shows that the 110 and 200 planes are merged to become a single broad peak. Field-emission scanning electron microscopy shows that the titanosilicate is spherical in shape and V2O5 has a hexagonal rod-shaped morphology. The presence of various metal ions, such as V, Ti, Si and O, was observed by energy dispersive X-ray analysis and X-ray photoelectron spectroscopy. The transmission electron microscopy image shows clear hexagonal mesoporous fringes with V2O5 distribution. The BET surface area analysis shows that the VTS catalysts have higher surface areas than pure V2O5. Fourier transform infrared spectroscopic analysis shows the presence of Ti4+ ions connected to the silanol groups. The bandwidths of pure titanosilicate, V2O5 and their composites were calculated from their diffuse reflectance ultraviolet-visible spectra. The bandwidth was tuned by heterojunctions in the studied catalysts. The photoluminescence spectra of the VTS catalysts show a distinct behaviour as compared to those of the pure components. The photocatalytic activity of methylene blue degradation was determined with pure constituents and catalysts. VTS-1 (TS and VO weight ratio 2 : 1) shows higher conversion than other catalysts, pure titanosilicate and V2O5. This is probably due to the heterojunctions and higher surface area in VTS-1. Kinetic studies reveal that direct sunlight shows higher activity than pure visible light. A plausible physical and chemical mechanism for the photocatalytic activity is proposed.