Rhodium-Catalyzed Enantioselective Synthesis,Structures, and Properties of Single and Double Azahelicene-Like Molecules

The enantioselective synthesis of aza[6] and [7]helicene-like molecules have been achieved by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed intramolecular [2+2+2] cycloaddition of cyanodiynes. This protocol was successfully applied to the diastereo- and enantioselective synthesis of an S-shaped double aza[6]helicene-like molecule with a high ee value of 89 %. Although no epimerization and racemization were observed in the double carbo[6]helicene-like molecule at 80 °C, epimerization and racemization of the double aza[6]helicene-like molecule proceeded at 80 °C. This double aza[6]helicene-like molecule showed good fluorescent quantum yields and chiroptical responses under both neutral and acidic conditions.     

Synthesis and Crystal Structure of Blue Luminescent Cadmium(II) Coordination Networks with 4,4′-Bis(imidazol-1-ylmethyl)biphenyl from Different Solvent Systems

Two supramolecular complexes, [Cd(bimb)²Cl²] (1) and [Cd(bimb)(DMF)Cl²]·DMF (2) [bimb=4,4′-bis(imidazol-1-ylmethyl)biphenyl], were synthesized by reactions of CdCl²·2.5H²O with bimb ligand in ethanol and N,N′-dimethylformamide (DMF), respectively, and their structures were determined by X-ray crystallography. Complex 1 is an infinite 2D grid network bridged by bimb ligands, and the 2D sheets were further linked by C–H ?Cl hydrogen bonds to form a polycatenated 3D framework. Complex 2 has dicadmium(II) di-μ-chloride units which are connected by bimb bridging ligands to form an infinite non-interpenetrating 2D network. The results provide a nice example of the solvent system exerting a great effect on the construction of supramolecular frameworks.     

The enhanced biological activities of three Zn (II) complexes based on different 1,2,4‐triazole fungicides

In order to screen effective fungicides, three Zn (II) complexes, [Zn L ¹ ₄ (NO₃)₂]·2H₂O·2EtOH ( 1 ), [Zn L ² ₄ (NO₃)₂] ( 2 ), and [Zn L ³ ₄ (DMF)₂](NO₃)₂ ( 3 ), ( L ¹  = paclobutrazol, L ²  = diniconazole, and L ³  = hexaconazole), were synthesized and characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal XRD. The antifungal activities of these complexes were then evaluated against four selected fungi using the mycelial growth rate method. The resulting data indicate that all the complexes show the enhanced antifungal activities than the corresponding ligand and mixtures. And, the interactions between the metal salt and ligands in the three complexes seem to be synergistic. According to the study of the influence of the structures on the activity, complex 2 with C=C linkage and 2,4‐dichlorophenyl moieties enhances the bioactivity significantly, especially against Wheat gibberellic ( II ). Density functional theory (DFT) calculations were carried out to help explain the enhanced bioactivity of the Zn (II) complexes. Meanwhile, all complexes are excellent grow‐regulators, especially complex 3 . The resulting data show that the complexes based on triazole fungicides have the potential applications in agriculture.     

Host–Guest Chemistry between Perylene Diimide (PDI) Derivatives and 18‐Crown‐6: Enhancement in Luminescence Quantum Yield and Electrical Conductivity

Perylene diimide (PDI) derivatives exhibit a high propensity for aggregation, which causes the aggregation‐induced quenching of emission from the system. Host–guest chemistry is one of the best‐known methods for preventing aggregation through the encapsulation of guest molecules. Herein we report the use of 18‐crown‐6 (18‐C‐6) as a host system to disaggregate suitably substituted PDI derivatives in methanol. 18‐C‐6 formed complexes with amino‐substituted PDIs in methanol, which led to disaggregation and enhanced emission from the systems. Furthermore, the embedding of the PDI ? 18‐C‐6 complexes in poly(vinyl alcohol) (PVA) films generated remarkably high emission quantum yields (60–70 %) from the PDI derivatives. More importantly, the host–guest systems were tested for their ability to conduct electricity in PVA films. The electrical conductivities of the self‐assembled systems in PVA were measured by electrochemical impedance spectroscopy (EIS) and the highest conductivity observed was 2.42×10^?5 S cm^?1.     

Hybrid EuIII Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence

In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent Ln^III-silica nanomaterials. A novel Eu^III-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)₃ (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)₃ was confirmed by ¹H, ³¹P, ²⁹Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)₃ and Eu(tfc)₃ moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)₃-modified silica nanoparticles, producing Eu(hfa)₃(TPPO−Si)₂-SiO₂ and Eu(tfc)₃(TPPO−Si)₂-SiO₂, respectively. Eu(hfa)₃(TPPO−Si)₂−SiO₂ exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported Eu^III-based hybrid materials. Eu(tfc)₃(TPPO−Si)₂−SiO₂ showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)₃(TPPO−Si(OEt)₃)₂ was found to be 39 %. These results confirmed that the TPPO−Si(OEt)₃ linker is a promising candidate for development of Eu^III-based luminescent materials.     

Preparation of Zn(Cd)O:Ga–SiO2 composite scintillating materials

Composite material consisting of highly luminescent Zn(Cd)O:Ga powder embedded in the silica matrix was prepared. It was found out that ZnO:Ga with less developed crystals (i.e. annealed at lower temperatures) is more prone to interact with the SiO₂ matrix and form zinc silicates, which in turn resulted in the decrease in the excitonic emission. Pre-annealing of the powders at temperatures above 600 °C prevented the interaction with the SiO₂ matrix. ZnO:Ga with well-developed crystals at such a high temperatures was not affected by the matrix and retained its properties, i.e. high radioluminescence intensity and ultrafast sub nanosecond photoluminescence decay. Introducing Cd into the ZnO lattice caused observable red shift in the excitonic luminescence, without negatively affecting the total intensity or the decay.     

Studies on interactions of excited cadmium and mercury atoms with secondary and tertiary alkyl- and silylamines in gas phase

The Cd(³P₁)- and Hg(³P₁)-photosensitized emissions of some secondary and tertiary alkyl- and silylamines have been investigated under conditions of steady illumination at 493 and 298 K, respectively. The emission bands were observed at around 440 nm in the cadmium-photosensitized reactions of these amines. In contrast, no appreciable emission bands were observed in the mercury-photosensitized reactions of these amines. However, upon addition of tert-butyl alcohol to the amine-mercury system, an emission band evolved at around 350 nm in the mercury-photosensitization. The peak-wavelengths for secondary and tertiary alkyl- and silylamines are slightly shorter than the values predicted from the correlations between the peak wavelength and the first ionization energy obtained in the cadmium- and mercury-photosensitized luminescence of ammonia and primary amines. The quenching efficiencies of the cadmium and mercury resonance lines by secondary alkyl- and silylamines are higher than those by tertiary alkyl- and silylamines. These observations suggest that the steric hindrance by the alkyl and silyl groups to the approach of the nitrogen atom in the amines to excited cadmium and mercury atoms seems to be an important factor for the stabilization of the exciplexes and the quenching of the resonance lines. The behavior of silylamines is similar to that of alkylamines in cadmium- and mercury-photosensitized reactions.