Ferrocene cored dendrimers incorporating anthracene capped furanoside branches: synthesis and photophysical studies

Dendrimers and dendrons having a ferrocene core and furanoside appended aromatic branches with peripheral anthracene units have been synthesised via convergent approaches. The study of their chiroptical and photophysical studies indicates amplification of chirality with increasing generations, and energy migration through arrayed anthracene units.     

Electrocatalytic treatment of waste: studies on discoloration of an industrial azo dye effluent

A textile dye effluent containing chiefly reactive azo dyes has been treated electrochemically for discoloration and COD (chemical oxygen demand) reduction at different current densities, flow rates and dilution. Experiments have been carried out in a thin electrochemical reactor under single pass conditions using a dimensionally stable catalytic anode (DSA) and a stainless steel cathode.     

Oxovanadium(IV) and -(V) complexes of dithiocarbazate-based tridentate Schiff base ligands: syntheses,structure, and photochemical reactivity of compounds involving imidazole derivatives as coligands

The tridentate dithiocarbazate-based Schiff base ligands H(2)L (S-methyl-3-((5-R-2-hydroxyphenyl)methyl)dithiocarbazate, R = NO(2), L = L(2); R = Br, L = L(3)) react with [VO(acac)(2)] in the presence of imidazole derivatives as coligands to form oxovanadium(IV) and cis-dioxovanadium(V) complexes. With benzimidazole and N-methylimidazole, the products are oxovanadium(IV) complexes, viz. [VOL(3)(BzIm)].0.5CH(3)CN (1a) and [VOL(N-MeIm)(2)] (L = L(3), 1b; L = L(2), 1c), respectively. In both 1a,b, the O and S donor atoms of the tridentate ligand are cis to the terminal oxo group (in the "equatorial" plane) and mutually trans, but the N donor atom is respectively cis and trans to the oxo atom, as revealed from X-ray crystallography. When imidazole or 4-methylimidazole is used as the ancillary ligand, the products obtained are water-soluble cis-dioxovanadium(V) complexes [VO(2)L(R'-ImH)] (L = L(3) and L(2), R' = H and Me, 2a-d). These compounds have zigzag chain structures in the solid state as confirmed by X-ray crystallographic investigations of 2a,d, involving an alternating array of LVO(2)(-) species and the imidazolium counterions held together by Coulombic interactions and strong hydrogen bonding. Complexes 2a-d are stable in water or methanol. In aprotic solvents, viz. CH(3)CN, DMF, or DMSO, however, they undergo photochemical transformation when exposed to visible light. The putative product is a mixed-oxidation divanadium(IV/V) species obtained by photoinduced reduction as established by EPR, electronic spectroscopy, and dynamic (1)H NMR experiments.     

First Bis(σ)-borane Complexes of Group 6 Transition Metals: Experimental and Theoretical Studies

A series of bis(σ)-borane complexes of Group 6 transition metals were prepared by direct dihydroborane coordination to the metal center. Reaction of [M(CO)₃(PCy₃)₂] and two dihydroboranes [DurBH₂] and [(Me₃Si)₂NBH₂] (Dur=2,3,5,6-Me₄C₆H) yielded bis(σ)-borane complexes fac-[M(CO)₃(PCy₃){η²-(H₂BR)}] (R=Dur; 1 : M=Cr, 2 : M=W; R=N(SiMe₃)₂; 3 : M=Cr, 4 : M=W). In the case of molybdenum, we have isolated an arene complex ( 5 ) with [DurBH₂] in which the Dur group acts as a η⁶-bound ligand, and with [(Me₃Si)₂NBH₂] a similar bis(σ)-borane complex was isolated, cis,trans-[Mo(CO)₂(PCy₃)₂{η²-(H₂BN(SiMe₃)₂}] ( 6 ), with a different pattern of auxiliary ligands. The complexes were investigated by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and computational methods. Quantum theory of atoms in molecules (QTAIM) calculations demonstrated that the borane complexes may be described as pure bis(σ)-borane complexes rather than elongated or stretched examples given that the calculations do not show the presence of a ring-critical point (RCP) at the ring formed by the interactions of the B−H with metal center.     

“Dial-In” Emission from a Unique Flexible Material with Polarization Tuneable Spectral Intensity

The development of organic photoluminescent materials, which show promising roles as catalysts, sensors, organic light-emitting diodes, logic gates, etc., is a major demand and challenge for the global scientific community. In this context, a photoclick polymerization method is adopted for the growth of a unique photoluminescent three-dimensional (3D) polymer film, E, as a model system that shows emission tunability over the range 350–650 nm against the excitation range 295–425 nm. The DFT analysis of energy calculations and π-stacking supports the spectroscopic observations for the material exhibiting a broad range of emission owing to newly formed chromophoric units within the film. Full polarization spectroscopic Mueller matrix studies were employed to extract and quantify the molecular orientational order of both the ground (excitation) and excited (emission) state anisotropies through a set of newly defined parameters, namely the fluorescence diattenuation and fluorescence polarizance. The information contained in the recorded fluorescence Mueller matrix of the organic polymer material provided a useful way to control the spectral intensity of emission by using pre- and post-selection of polarization states. The observation was based on the assumption that the longer lifetime of the excited dipolar orientation is attributed to the compactness of the film.     

Thermally exfoliated graphene oxide reinforced stress responsive conductive nanocomposite hydrogel

Lightweight and flexible biosensors that can sustain mechanical deformation and can be adhered to human skin is an interesting field of study. In the current article, a systematic study on development of thermally exfoliated graphene oxide (TEGO)–reinforced poly(vinyl alcohol) (PVA)–based conductive hydrogel nanocomposites has been reported. The free‐standing hydrogels were synthesized using controlled and repetitive freeze‐thaw cycles. The samples were then studied for their mechanical as well as electrical properties. The hydrogels were characterized for their microstructural, chemical, and rheological properties to understand the observed macroscopic properties. Additionally, a study on the behavior of hydrogels immersed in phosphate‐buffered saline (PBS) was carried out to investigate their hydrolytic stability within simulated biological environment. Overall, the nanocomposite hydrogels demonstrated excellent static and dynamic mechanical performance, stability in PBS, considerable electrical conductivity, and significant electrical response to applied external stress, establishing their potential for use as flexible biosensors.     

Hydrogen‐Bonding‐Regulated Supramolecular Nanostructures and Impact on Multivalent Binding

Herein we describe the H‐bonding‐regulated nanostructure, thermodynamics, and multivalent binding of two bolaamphiphiles NDI‐1 and NDI‐2 consisting of a hydrophobic naphthalene diimide connected to a hydrophilic wedge by a H‐bonding group and a glucose moiety on its two arms. NDI‐1 and NDI‐2 differ by the single H‐bonding group, namely, hydrazide or amide, which triggers the formation of vesicles and cylindrical micelles, respectively. Although the extended H‐bonding ensures stacking with head‐to‐head orientation and the formation of an array of the appended glucose moieties in both systems, the adaptive cylindrical structure exhibited superior multivalent binding with concanavalin A (ConA) to that of the vesicle. A control amphiphile lacking a H‐bonding group assembled with a random lateral orientation to produce spherical micelles without any notable multivalent binding.     

Camouflaging Structural Diversity: Co‐crystallization of Two Different Nanoparticles Having Different Cores But the Same Shell

Two ligand‐protected nanoscale silver moieties, [Ag₄₆(SPhMe₂)₂₄(PPh₃)₈](NO₃)₂ and [Ag₄₀(SPhMe₂)₂₄(PPh₃)₈](NO₃)₂ (abbreviated as Ag₄₆ and Ag₄₀, respectively) with almost the same shell but different cores were synthesized simultaneously. As their external structures are identical, the clusters were not distinguishable and become co‐crystallized. The occupancy of each cluster was 50 %. The outer shell of both is composed of Ag₃₂S₂₄P₈, which is reminiscent of fullerenes, and it encapsulates a well‐studied core, Ag₁₄ and a completely new core, Ag₈, which correspond to a face‐centered cube and a simple cube, respectively, resulting in the Ag₄₆ and Ag₄₀ clusters. The presence of two entities (Ag₄₀ and Ag₄₆ clusters) in a single crystal and their molecular formulae were confirmed by detailed electrospray ionization mass spectrometry. The optical spectrum of the mixture showed unique features which were in good agreement with the results from time‐dependent density functional theory (TD‐DFT).     

Influence of pyridine oximate and quaternized pyridinium oximate ions on the hydrolysis of phosphate esters in cationic microemulsions

Kinetic studies have been performed to understand the hydrolytic potencies of oximate (2- and 4-pyridinealdoxime) and its functionalized oximate (4-(hydroxyiminomethyl)-1-alkylpyridinium bromide) ions (alkyl?=?C₁₀H₂₁ (4-C₁₀PyOx^-); alkyl?=?C₁₂H₂₅ (4-C₁₂PyOx^-)) in the cleavage of phosphate esters, diethyl p-nitrophenylphosphate (Paraoxon) and p-nitrophenyl diphenyl phosphate (PNPDPP) in a cationic (O/W) microemulsion system (ME) over a pH range 7.5 to 11.0 at 300?K. The k_obs values for the reaction of paraoxon with oximate and its functionalized oximate were determined in different microemulsion composition and the kinetic rate data shows that k_obs values increases with increasing water content. The specificity of different chain length of alcohols (n-butanol, n-pentanol, n-hexanol and n-octanol) was also investigated in hydrolytic reactions of paraoxon for different microemulsion composition.     

A unified,RCM anchored approach to spiro[4.5]decane-based sesquiterpenoids: Collective synthesis of (±)-α & β-vetispirenes, (±)-β-vetivone, (±)-agarospirol and (±)-hinesol

Collective syntheses of five spiro[4.5]decane framework bearing sesquiterpenoids, namely, α & β-vetispirenes, β-vetivone, agarospirol and hinesol as well as formal synthesis of axenol and gleenol from a readily available precursor cyclohexanone-β-ketoester via the intermediacy of a versatile intermediate (2,10-dimethylspiro[4.5]dec-1-en-6-one) have been accomplished in a concise manner.