The HOMO Nodal Arrangement in Polychromophoric Molecules and Assemblies Controls the Interchromophoric Electronic Coupling

Triptycenes spontaneously assemble into two‐dimensional networks in which long‐range charge transport is facilitated by the extensive electronic coupling through the triptycene framework (intramolecularly) and by cofacial π‐stacking (intermolecularly). While designing and synthesizing next‐generation triptycenes containing polyaromatic chromophores, the electronic coupling amongst the chromophores was observed to be highly dependent on the nature and position of the substituents. Herein, we demonstrate using hexaalkoxytriptycenes that the electronic coupling amongst the chromophores is switched on and off by a simple repositioning of the substituents, which alters the nodal arrangement of the HOMOs of the individual chromophores. A visual inspection of the HOMOs can thus provide a ready evaluation of the electronic coupling in polychromophoric molecules/assemblies, and will serve as an important tool for the rational design of modern charge‐transport materials.     

HYDROXYALKANESULFONYL CHLORIDES FROM CHLORINATION OF HYDROXYALKANESULFINATE SALTS IN A NONPOLAR MEDIUM: 3-HYDROXY-1-PROPANESULFONYL AND 4-HYDROXY-1-BUTANESULFONYL CHLORIDES

Abstract

3-Hydroxy-1-propanesulfonyl chloride (1b) was obtained for the first time (admixed with 10% of propane sultone, 2b) by chlorination of a dichloromethane suspension of sodium 3-hydroxy-1-propanesulfinate (3b). 4-Hydroxy-1-butanesulfonyl chloride (1c) containing 13% butane sultone (2c) was prepared similarly from 3c. The cyclizations of 1b and 1c in CDCl₃ containing 1-butanol (0.9 M) showed first order rate constants of 1.4 × 10^?4 and 6.4 × 10^?5 s^?1, corresponding to effective concentrations of 4.5 × 10² and 2.1 × 10² M, respectively. Reaction of triethylamine in ethanol-d (a) with 1b gave exclusively the undeuterated sultone (2b), evidently by a direct cyclization, and (b) with 1c produced mainly ethyl 4-hydroxy-1-butanesulfonate largely monodeuterated at the α-position, and presumably formed by way of the sulfene (6c).     

Effect of increasing temperature due to depletion of ozone layer caused by CFC on the dynamics of two competing populations: a model

It is well recognized that the greenhouse gas such as Chlorofluoro Carbon (CFC) is responsible for the increase in the average global temperature. The presence of CFC is responsible for the depletion of ozone concentration in the atmosphere due to which the heat accompanied with the sun rays are less absorbed causing increase in the atmospheric temperature of the Earth. The increase in temperature level may directly or indirectly affect the dynamics of interacting species systems. Therefore, in this paper, a mathematical model is proposed and analysed to asses the effects of increasing temperature on the survival or extinction of two competing populations.     

Effect of environmental temperature and applied potential on water desalination performance using electrodialysis

Desalination of brackish water is a challenging task for higher recovery of water. In most of the cases, water recovery is low with high wastage. Electrodialysis (ED) provides a solution of water desalination with high recovery. Ion-exchange membranes are the main component for electrodialysis system. Here cation-exchange membrane and anion-exchange membrane were synthesized by free-radical polymerization for water desalination by ED. ATR-FTIR confirms the successful functionalization of the membranes and scanning electron microscopy technique reveals the dense morphology of the membranes. Here we used polyethylene as a binder and blow film extrusion for film formation, which is not only economically viable as well as large amount of membranes can be produced without using hazardous solvent. The desalination study reveals the improvement in desalination performance with slight increment in temperature which may be due to higher ionic mobility. The mechanical and thermal stability of the membranes was characterized to ensure the viability of membranes for desalination at higher temperatures. Effect of applied potential was also studied in the removal of pathogens during desalination and confirmed that 2 V/cell pair applied potential removes almost 97% pathogens during desalination in continuous mode.     

Cooperative C-H…N and C-H…π bonded molecular dimers of 5-aryl-7,8,13,14-tetrahydro-dibenzo[a,i]phenanthridine

As a result of our new high-yielding one-pot reaction procedure, the investigation on a series of heterocyclic 5-aryl-7,8,13,14-tetrahydro-dibenzo[a,i]phenanthridine compounds was possible and reported: 5-(4-ethyl-phenyl)-7,8,13,14-tetrahydro-dibenzo[a,i]phenanthridine, 5-(4-cyano-phenyl)-7,8,13,14-tetrahydro-dibenzo[a,i]phenanthridine, and 5-(2-ethyl-phenyl)-7,8,13,14-tetrahydro-dibenzo[a,i]phenanthridine. Half-chair conformation of alicyclic rings gives rise to a slightly folded structure of central tricyclic phenanthridine. The structure analysis showed the formation of a well-defined dimeric unit in the crystals. Dimeric association essentially involves cooperative C-H…N and C-H…π close contacts between molecules related by a center of inversion. The first two compounds are isomorphous with noticeable differences in steric packing. The first structural elucidation on 5-aryl-7,8,13,14-tetrahydro-dibenzo[a,i]phenanthridine compounds indicates the prominent mode of interactions, which has use in structure-based drug discovery and optoelectronic applications.     

Azabicyclo[3.3.1]nonanone: a case when weak interactions are preferred over strong hydrogen bonds

Derivatives of azabicyclo[3.3.1]nonanone tend to prefer for weak interactions in the crystal over strong N–H···O hydrogen bonds. The main stabilizing forces in the investigated azatricyclo[7.3.1.0^2,7]trideca-trienone derivatives are C–H···O, N–H···π and C–H···π interactions, leading to interesting structural patterns. The azabicyclo[3.3.1]nonanone ring adopts chair-envelope conformation having exo-C2,C4-aromatic substituents. Amino NH is in trigonal pyramidal configuration. The interesting stereochemistry of azabicyclo[3.3.1]nonanone, driving exceptional preference for weaker interactions over strong hydrogen bonds serves a useful example toward engineering and design strategy, and structure prediction methodologies.     

Asymmetric synthesis of (−)-tetrahydrolipstatin

Attempts toward the asymmetric synthesis of (−)-tetrahydrolipstatin are described. A palladium catalyzed Wacker-type reaction to convert an alkene to a ketone, highly diastereoselective reduction of a β-hydroxy ketone, selective oxidation of a diol, and modular synthesis are the key features of the successful approach.     

Evaluation of specific heat and related thermodynamic properties of Ge1?xSnxSe2.5 (0?≤?x?≤?0.5) glasses

This paper presents the result of thermodynamic studies on Ge_1−x Sn _x Se_2.5 (0 ≤ x ≤ 0.5) glasses using differential scanning calorimetry. The obtained experimental results on phase transformations have been employed to obtain thermodynamic parameters like entropy difference between metastable states in the glassy region, difference of Gibbs free energy, specific heat, entropy between the glassy and the crystalline phase and the enthalpy released during phase transformation (glassy to crystalline). The results yield that, Ge_0.7Sn_0.3Se_2.5 sample is least stable among all the samples. The stability increases on addition of Sn beyond 0.3 at. mass% upto 0.5 at. mass%.     

Synthesis and characterization of glycol-modified vanadium(V) oxoisopropoxide and their oximato derivatives: sol–gel transformations of [VO(OPr i )3], [VO{OCH2CH2OCH2CH2O}{OPr i }] and [VO{OCH2CH2OCH2CH2O}{ON=C(CH3)(C4H3S-2)}] to vanadia

Reaction of [VO(OPr ⁱ )₃] (1) with [O(CH₂CH₂OH)₂] in 1:1 molar ratio in anhydrous benzene yield glycol-modified precursor, [VO{OCH₂CH₂OCH₂CH₂O}{OPr ⁱ }] (2). Further reactions of (2) with internally functionalized oximes in anhydrous benzene yield heteroleptic complexes of the type [VO{OCH₂CH₂OCH₂CH₂O}{ON=C(R)(Ar)}] (3–8) {where R=CH₃, Ar=C₄H₃O-2 (3), C₄H₃S-2 (4), C₅H₄N-2 (5); and when R=H, Ar=C₄H₃O-2 (6), C₄H₃S-2 (7), C₅H₄N-2 (8)}. All these derivatives have been characterized by elemental analyses, molecular weight measurements and spectroscopic techniques. The crysoscopic molecular weight measurement as well as FAB mass study suggests dimeric nature of (2). However, FAB mass spectrum of (4), and the crysoscopic molecular weight measurements of (3), (4), (5) and (6) indicate the monomeric behavior of the oximato derivatives (3–8). Hexa-coordination around vanadium(V) has been proposed for both monomeric and dimeric derivatives. Sol–gel transformations of (1), (2) or (4) to vanadia [(a), (b) or (c), respectively] have been carried out at low sintering temperature (600 °C). The XRD patterns of (a), (b) or (c) indicate formation of a single orthorhombic phase in all the three cases. The SEM images suggest grain like [for (a) and (b)] and rod like [for (c)] morphology of the crystallites. IR, Raman spectra as well as EDX analyses indicate formation of pure vanadia. Absorption spectra of the vanadia (b) and (c) suggest energy band gaps of 2.53 and 2.65 eV, respectively.