New Routes to a Series of σ‐Borane/Borate Complexes of Molybdenum and Ruthenium

A series of agostic σ‐borane/borate complexes have been synthesized and structurally characterized from simple borane adducts. A room‐temperature reaction of [Cp*Mo(CO)₃Me], 1 with Li[BH₃(EPh)] (Cp*=pentamethylcyclopentadienyl, E=S, Se, Te) yielded hydroborate complexes [Cp*Mo(CO)₂(μ‐H)BH₂EPh] in good yields. With 2‐mercapto‐benzothiazole, an N,S‐carbene‐anchored σ‐borate complex [Cp*Mo(CO)₂BH₃(1‐benzothiazol‐2‐ylidene)] ( 5 ) was isolated. Further, a transmetalation of the B‐agostic ruthenium complex [Cp*Ru(μ‐H)BHL₂] ( 6 , L=C₇H₄NS₂) with [Mn₂(CO)₁₀] affords a new B‐agostic complex, [Mn(CO)₃(μ‐H)BHL₂] ( 7 ) with the same structural motif in which the central metal is replaced by an isolobal and isoelectronic [Mn(CO)₃] unit. Natural‐bond‐orbital analyses of 5–7 indicate significant delocalization of the electron density from the filled σ_B?H orbital to the vacant metal orbital.     

X-ray and optical studies of an isothiocyanato liquid crystal mixture

In this work, X-ray and optical studies have been carried out on a four-component isothiocyanato liquid crystal mixture with laterally substituted fluorine atoms. Molecular characteristics, such as effective inter molecular distances and apparent molecular length of the average-simulated molecule have been determined from X-ray studies at various temperatures in the liquid crystalline phase. From the nature of molecular alignment as envisaged from X-ray photographs, the orientational order parameter and its variation with temperature have been determined. Optical studies have also been conducted at various temperatures to investigate the thermal variations of birefringence. Macroscopic orientational order parameter and its thermal variation have been determined from these studies. The nature of order parameter variation obtained from the two studies, X-ray and optical have been compared.     

Nanowires of metal-organic complex by photocrystallization: a system to achieve addressable electrically bistable devices and memory elements

A new method has been achieved to form a Cu:benzoquinone derivative (DDQ) charge-transfer complex by the photoexcitation of [Cu(DDQ)2(CH 3COO)2] ( 1) that has been synthesized by the reaction of DDQ and hydrated cupric acetate in acetonitrile. Photoexcitation of coordinated complex 1 leads to the formation of charge-transfer complex Cu2+(DDQ(.-)2 ( 2). The charge transfer complex 2, when spun on solid substrates, forms nanowires. Sandwich structures of 2 exhibit electrical bistability associated with memory phenomenon. Read-only and random-access memory phenomena are evidenced in nanowires of 2 providing a route to attend the issues pertaining to the addressibility of organic memory devices.     

A new organic compound for the synthesis of gold nanoparticles

2,3,5,6-Tetrakis-(morpholinomethyl)hydroquinone (1) is used for the first time in the preparation of gold nanoparticles by the reduction of HAuCl₄ in water–methanol medium without using any capping agent. Compound 1 was prepared by Mannich-type aminomethylation of hydroquinone with morpholine. It is characterized by elemental analysis, FT-IR, UV–Vis and mass spectra and finally by single crystal X-ray diffraction. The ratio of HAuCl₄ and compound 1 played a vital role in controlling the shape and size of gold nanoparticles. The samples were characterized by Transmission Electron Microscopy (TEM), XRD, FT-IR, UV–Vis measurements. With the increasing amount of gold(III) solution with respect to compound 1, two different morphologies such as self-assembled and spherical gold nanoparticles have been observed. The results indicate that the morphology of gold nanoparticles with different sizes can be controlled by changing the concentrations of compound 1 and gold(III) solution.     

Size selective self-sorting in coordination-driven self-assembly of finite ensembles

Size selective self-sorting in the coordination-driven self-assembly of two-dimensional (2-D) polygons and three-dimensional (3-D) cages is presented. Two types of polygons (rectangular and triangular) of different size are formed spontaneously from within mixtures of a molecular "clip" or a 60 degrees organoplatinum acceptor with dipyridyl linkers of different lengths via self-sorting. Furthermore, two different sized 3-D supramolecular cages are formed upon mixing one ditopic organoplatinum acceptor and two different sized tritopic donors from the self-sorting process. The formation of these polygons and cages is characterized using NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). In all cases, the self-sorting process is directed by the size of the donor building blocks and a dynamic, thermodynamically driven self-correction process resulting in the formation of discrete products from complex mixtures.     

A highly selective fluorescent chemosensor for zinc ion and imaging application in living cells

A new 2,6-bis(5,6-dihydrobenzo[4,5]imidazo[1,2-c]quinazolin-6-yl)-4-methylphenol (1) serves as a highly selective and sensitive fluorescent probe for Zn(2+) in a HEPES buffer (50 mM, DMSO:water = 1:9 (v/v), pH = 7.2) at 25 °C. The increase in fluorescence in the presence of Zn(2+) is accounted for by the formation of dinuclear Zn(2+) complex [Zn(2)(C(35)H(25)N(6)O)(OH)(NO(3))(2)(H(2)O)] (2), characterized by X-ray crystallography. The fluorescence quantum yield of the chemosensor 1 is only 0.019, and it increases more than 12-fold (0.237) in the presence of 2 equiv of the zinc ion. Interestingly, the introduction of other metal ions causes the fluorescence intensity to be either unchanged or weakened. By incubation of cultured living cells (A375 and HT-29) with the chemosensor 1, intracellular Zn(2+) concentrations could be monitored through selective fluorescence chemosensing.     

A study of the thermal properties of single jersey fabrics of cotton, bamboo and cotton/bamboo blended-yarn vis-a-vis bamboo fibre presence and yarn count

In this study, the thermal properties of 100% cotton, 50/50 cotton/bamboo and 100% bamboo single jersey fabrics with differing yarn linear density are evaluated and analysed. The linear densities of the yarns composing the fabrics are 20^s, 25^s, 30^s Ne_c and the twist level in the yarns is kept the same. An increasing the presence of bamboo fibre in the fabric causes a reduction in fabric thickness and GSM for all linear densities of yarn. Air permeability and water-vapour permeability also increase with increase in bamboo fibre content while both thermal conductivity and thermal resistance show a decreasing trend. As the constituent yarn gets finer, fabric air and water-vapour permeability both increase in value while the thermal conductivity falls.     

Syntheses and tunable emission properties of 2-alkynyl azulenes

Various substituted 2-azulenes have been synthesized via Sonogashira coupling. Doping with superacids allows tunable emission from 443 to 750 nm depending on the substitution. The proton doped compounds are the first azulene alkyne based systems that show emission originating only from the S(1) excited state.