Pillar[5]arene based conjugated macrocycle polymers with unique photocatalytic selectivity

The development of heterogeneous catalysts with substrate shape, size or electronic constitution selectivity is a huge challenge in photocatalysis. Reported herein is a host-guest interaction strategy to endow photocatalysts with special selectivity. By adjusting the precursors, conjugated macrocycle polymers (CMPs) with pillar[5]arene struts (CMP-1 and CMP-2) and a corresponding non-pillar[5]arene-contained conjugated organic polymer (COP-1) were prepared and the photocatalytic activities toward sulfide derivatives were investigated. The sulfides showed similar conversions when COP-1 was used as a photocatalyst, but exhibited significant differences when it turned to the CMPs. Remarkably, the conversion yield of S-1 achieved near 18 folds over the one of S-2 when CMP-2 was used as a catalyst. Mechanism studies confirmed that the “host-guest” effect of pillar[5]arene struts in CMPs was the main cause of the difference. The present work establishes CMPs as novel heterogeneous photocatalysts with substrate selectivity, and such a method will inspire the researchers concerning preparation of heterogeneous catalysts with excellent selectivity.     

Organophosphine/phosphite‐stabilized silver(I) complexes bearing N‐acetylbenzamide ligand: synthesis,characterization and potential application in metal organic chemical vapor deposition

New N‐silver(I) acetylbenzamide complexes of type L_n?AgNC₉H₈O₂ (L = PPh₃; n = 1, 2a; n = 2, 2b; n = 3, 2c; L = P(OEt)₃; n = 1, 2d; n = 2, 2e; n = 3, 2f) were prepared. These complexes were obtained in high yields and characterized by elemental analysis, ¹H NMR, ¹³C{H} NMR, ³¹P{H} NMR and IR spectroscopy, respectively. The molecular structure of 2b has been determined by X‐ray single‐crystal analysis in which the silver atom is in a distorted tetrahedral geometry and crystallizes as cis–trans. New N‐silver(I) acetylbenzamide complexes have a four‐membered ring, which could influence their chemical and physical properties and modulate volatility. Metal organic chemical vapor deposition experiments were carried out successfully at 400°C and 450°C using 2e as precursor for the deposition of silver films, respectively. The high‐purity silver film obtained at 400°C is dense and homogeneous. Copyright © 2012 John Wiley & Sons, Ltd.     

Concurrent Covalent and Supramolecular Polymerization

Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy—namely, one which utilizes 1) a bis‐azide‐functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis‐alkyne‐functionalized biphenyl derivative in one dimension as a result of a rapid and efficient β‐cyclodextrin(CD)‐accelerated, cucurbit[6]uril(CB)‐templated azide–alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss‐cross fashion by dint of π–π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Novel ether-functional spiro-tetronic acid derivatives: molecule design, convenient synthesis and biological evaluation

A novel series of ether functionalization of spiro-tetronic acid derivatives have been designed and conveniently synthesized via three steps, including esterification, one-pot heterocyclization, and etherification reactions. The target molecules have been identified on the basis of analytical spectra data. All newly synthesized compounds have been screened for their potential insecticidal activity against Heliothis armigera and Plutella xylostella compared with spirodiclofen by standard method.     

Solution-processable graphenes by covalent functionalization of graphene oxide with polymeric monoamines

We develop here a simple wet chemistry to prepare covalent functionalized graphenes(FGs) through epoxide aminolysis especially under alkaline aqueous condition. Remarkably, a series of typical monoamines, such as industrial Huntsman Jeffamine~ M-2070 and M-2005 polymer with hydrophilic or hydrophobic polyetheramine chains, positively-charged 2-amino-N,N,Ntrimethylpropanaminium,negatively-charged sulfanilic acid, even oligopeptide sequence, can be effectively grafted on the platelets of graphene oxide precursor with covalent functionalization and partially reduced features. This strategy provides the researchers a facile and convenient approach to design and synthesize solution processable, biocompatible and functionalized graphenes for the potent applications in electronic inks, drug carriers and biomedicines. Expansion of the current study is actively ongoing in our laboratory.