Bidirectional and unidirectional PCET in a molecular model of a cobalt-based oxygen-evolving catalyst

The oxidation of water to molecular oxygen is a kinetically demanding reaction that requires efficient coupling of proton and electron transfer. The key proton-coupled electron transfer (PCET) event in water oxidation mediated by a cobalt-phosphate-based heterogeneous catalyst is the one-electron, one-proton conversion of Co(III)-OH to Co(IV)-O. We now isolate the kinetics of this PCET step in a molecular Co(4)O(4) cubane model compound. Detailed electrochemical, stopped-flow, and NMR studies of the Co(III)-OH to Co(IV)-O reaction reveal distinct mechanisms for the unidirectional PCET self-exchange reaction and the corresponding bidirectional PCET. A stepwise mechanism, with rate-limiting electron transfer is observed for the bidirectional PCET at an electrode surface and in solution, whereas a concerted proton-electron transfer displaying a moderate KIE (4.3 ± 0.2), is observed for the unidirectional self-exchange reaction.     

Visible Colorimetric Sensor for Fluoride Ion Based on o-Phenylenediamine

A new chromogenic receptor based on 1,2-phenylene derivative containing thiourea moieties is synthesized and examined for its anion binding ability by UV–Vis and ¹H NMR studies. The results show that the receptor has selective colorimetric sensing of fluoride over all other anions like chloride, bromide, iodide, nitrate, hydrogen sulphate and acetate.     

Clouding and Hydrodynamic Behavior of Pluronic-Surfactant Interaction in Aqueous Salt Solutions

Clouding behavior of PEO-PPO-PEO and PPO-PEO-PPO block copolymers were studied in presence of sodium dodecyl sulfate (SDS) and NaCl. Extensive study of Pluronic P84 (EO₁₉PO₄₃EO₁₉) with different salts and ionic surfactants, were carried out using cloud point, viscosity and dynamic light scattering (DLS) measurements. The change in cloud point, as well as the size of P84 micelles in aqueous salt solution obeys the Hofmeister lyotropic series. Results on P84-ionic surfactant mixture indicate stronger interaction in case of SDS compared to those in presence of dodecyl trimethylammonium chloride (DTAC); here interaction seems to diminish in the presence of salts.     

Tetraphenylethene‐Based Conjugated Fluoranthene: A Potential Fluorescent Probe for Detection of Nitroaromatic Compounds

This study reports the synthesis and photophysical properties of a star‐shaped, novel, fluoranthene–tetraphenylethene (TFPE) conjugated luminogen, which exhibits aggregation‐induced blue‐shifted emission (AIBSE). The bulky fluoranthene units at the periphery prevent intramolecular rotation (IMR) of phenyl rings and induces a blueshift with enhanced emission. The AIBSE phenomenon was investigated by solvatochromic and temperature‐dependent emission studies. Nanoaggregates of TFPE, formed by varying the water/THF ratio, were investigated by SEM and TEM and correlated with optical properties. The TFPE conjugate was found to be a promising fluorescent probe towards the detection of nitroaromatic compounds (NACs), especially for 2,4,6‐trinitrophenol (PA) with high sensitivity and a high Stern–Volmer quenching constant. The study reveals that nanoaggregates of TFPE formed at 30 and 70 % water in THF showed unprecedented sensitivity with detection limits of 0.8 and 0.5 ppb, respectively. The nanoaggregates formed at water fractions of 30 and 70 % exhibit high Stern–Volmer constants (K_sv=79 998 and 51 120 m ^?1, respectively) towards PA. Fluorescence quenching is ascribed to photoinduced electron transfer between TFPE and NACs with a static quenching mechanism. Test strips coated with TFPE luminogen demonstrate fast and ultra‐low‐level detection of PA for real‐time field analysis.     

Isomerization dynamics and control of the eta2/N equilibrium for pyridine complexes

A series of pyridine complexes are prepared of the general form TpW(NO)(PMe3)(pyr) where pyr is either pyridine or a substituted pyridine. Depending on substitution pattern, the pyridine can be either N- or eta2-coordinated, and the role of the pyridine substituents and metal oxidation state in determining this equilibrium is explored. For eta2-pyridine complexes, the substituent pattern and solubility characteristics also determine the ratio of coordination diastereomers. Rates of both intra- and interfacial linkage isomerizations are explored along with the pyridine rotational barrier. This study is supported by DFT calculations and X-ray data and includes characterization of both eta2-pyridine and eta2-pyridinium complexes.     

Fluoride triggered fluorescence "turn on" sensor for Zn2+ ions based on pentaquinone scaffold that works as a molecular keypad lock

A pentaquinone based compound 3a has been synthesized which exhibits pronounced fluorescence enhancement in the presence of Zn(2+) ions under a F(-) triggered synergistic effect. Derivative 3a also behaves as a molecular keypad lock with sequential chemical inputs of Zn(2+) and F(-) ions.     

Studies on the Preparation and Properties of Thiol Derivatives of Biscyclopentadienyl Molybdenum (VI) and Bisindenyl Molybdenum (VI) Oxide Dichloride

Biscyclopentadienyl molybdenum (VI) oxide dichloride (I) and bisindenyl molybdenum (VI) oxide dichloride (II) react with various thiols in tetrahydrofuran and from the complexes of the type (C₃H₅)₂MoO (R₂) and (C₉H₇)₂MoO (R₂) wherein R may be S CH₈, S C₂H₅, S C₃H^N₇, S C₃H₇, S C₄Hⁿ₉, or S C₄H₃ or S C₃H₁₁. The preparation, thermal stabilities, physical characteristics and infrared spectra of these complexes have been studied in this paper.     

Optical chemosensor for Ag+, Fe3+, and cysteine: information processing at molecular level

A thiacalix[4]arene based chemosensor 3 bearing two pyrene groups has been synthesized which demonstrates ratiometric sensing with Ag(+) and fluorescence quenching with Fe(3+) ions in mixed aqueous media. The 'in situ' prepared Ag(+) and Fe(3+) complexes showed high selectivity toward cysteine. The molecular switching between three chemical inputs (Ag(+), Fe(3+), cysteine) results in various molecular logic gates which have been integrated sequentially to generate a sequential information processing device.     

Alkoxide Derived SrBi2Ta2O9 Phase Pure Powder and Thin Films

Phase pure powder and thin films of the novel ferroelectric materials SrBi₂Ta₂O₉ (SBT) have been prepared using the organic precursors. The xero-gel formed was dried and characterized using TGA and DTA to determine the organic burn out and crystallization temperature of SBT. Powder X-ray diffraction was used systematically to check the crystallinity of SBT. Phase pure SBT powder was formed as low as 650°C and thin films at 600°C in comparison to other earlier reported work. SEM micrographs show a grain size of ≈0.1 μm and show crack free films with a film thickness of 2 μm.