Complexation of phenolic guests by endo- and exo-hydrogen-bonded receptors

This article describes the complexation of phenol derivatives by hydrogen-bonded receptors. These phenol receptors are formed by self-assembly of calix[4]arene dimelamine or tetramelamine derivatives with 5,5-diethylbarbiturate (DEB) or cyanurate derivatives (CYA). The double rosette assemblies 3(3).(DEB)6/(CYA)6 have their phenol-binding functionalities (ureido groups) at the top and at the bottom of the double rosette (exo-receptors). The tetrarosette assemblies 4(3).(DEB)12/(CYA)12 form a cavity with binding sites between the two double rosettes for guest encapsulation (endo-receptors). An intrinsic binding constant Ka of 202 M-1 and 286 M-1 for the binding of 4-nitrophenol to the ureido functionalized exo- and endo-receptors, respectively, was observed. For the exo-receptor a 1:6 stoichiometry was observed while for the endo-receptor 1:4 binding stoichiometry was determined by Job plot and MALDI-TOF MS. The important role that the hydroxy group's acidity plays in the complexation of 4-nitrophenol is clarified by binding studies with different phenol derivatives. The hydrogen-bonded receptors showed a much smaller response towards less acidic phenol derivatives.     

Proton-sensitive fluorescent organogels

A 1,10-phenanthroline-appended cholesterol-based gelator (1) and its nongelling reference compound (2) were synthesized. Among 19 solvents tested herein, gelator 1 could gelate 11 solvents including alcohols, dipolar aprotic solvents, organic acids and a base (triethylamine), indicating that 1 acts as a versatile gelator. The TEM observation gave a visual image showing that fibrillar aggregates are entangled in the three-dimensional network structure. In the fluorescence measurements, most gels afforded an emission maximum at 394 nm (purple emission), whereas only the acetic acid gel afforded an emission maximum at 522 nm (yellow emission). Thus, the influence of protonation of the 1,10-phenanthroline nitrogens (by trifluoroacetic acid) on the fluorescence properties in the gel phase was investigated in detail. The results have established that the fluorescence intensity of 1 x H+ becomes particularly strong in the gel phase, presumably because of the energy transfer from neutral 1* to protonated 1 x H+ and the restriction of the 1 x H+ molecular motion. The finding suggests the possibility that the gel system would be useful not only as a new proton-sensitive fluorescence system but also as a new medium for designing efficient energy transfer systems.     

α‐Chiral Acetylenes Having an All‐Carbon Quaternary Center: Phase Transfer Catalyzed Enantioselective α Alkylation of α‐Alkyl‐α‐alkynyl Esters

Going through the phases : The title reaction was found to proceed by an initial base‐mediated isomerization to allenyl esters and subsequent phase transfer catalyzed alkylation at the α position of the ester (see scheme).

     

Aggregated structure analysis of polymer-protected platinum/ruthenium colloidal dispersions using EXAFS, HRTEM, and electron diffraction measurements

Polymer-protected platinum/ruthenium colloidal dispersions were prepared by refluxing mixed solutions of hexachloroplatinic(IV) acid and ruthenium(III) chloride in a mixture of ethanol/water (1/1 v/v) in the presence of poly(N-vinyl-2-pyrrolidone). The electronic spectra and transmission electron micrographs suggested that the colloidal dispersions are almost composed of the mixture of the small monometallic Pt and Ru clusters over all the ratio of Pt/Ru compositions. Extended X-ray absorption fine structure analyses and high resolution electron microprobe analyses indicated that no Pt/Ru alloy clusters exist in the dispersions, and the aggregation occurs between small monometallic Pt clusters (diameter ca. 15 A) and partially oxidized Ru microclusters (diameter less than 10 A). Electron diffraction measurements also suggested that the diffraction pattern of aggregated Pt/Ru cluster particles prepared by the simultaneous reduction of Pt and Ru ions is the same as that of the physical mixture of the small monometallic Pt and Ru clusters separately prepared. Therefore, it can be concluded that the aggregated Pt/Ru cluster particles, with 10 to 60 A in diameter, are built up by small monometallic Pt clusters and partially oxidized Ru microclusters, and that Pt/Ru alloy clusters are not formed.