A sustainable four-step synthesis of soluble perylenophanes for applications as fluorescent optical functional materials is presented and even allows upscaling because of starting with technical bulk products. Thus, t...A sustainable four-step synthesis of soluble perylenophanes for applications as fluorescent optical functional materials is presented and even allows upscaling because of starting with technical bulk products. Thus, terminal alkenylnitriles were alkylated reduced to amines, condensed with perylenetetracarboxylic bisanhydride and cyclised to cyclophanes by means of double cross metathesis in yields until 69% of isolated dyes. The first metathesis by means of the second-generation Hoveyda-Grubbs-catalyst brings the remaining reactive olefinic groups close together favouring the ring-closure to the cyclophanes where the locked neighboring of chromophores in a skew arrangement induce strong exciton interactions. The latter cause an increased the Stokes’ separation by means of a moderate hypsochromic shift of light absorption and a stronger bathochromic shift of fluorescence. Various applications such as for lasers, photonics, solar collectors or in analytics are discussed.展开更多
A new non-covalently bonded 3D supramolecular architecture,namely,[Cd^(Ⅱ)_(2)Cl_(2)(μ-Cl)_(2)(μ-L)]n[where L=1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane]was synthesized and structurally characterized.In this ...A new non-covalently bonded 3D supramolecular architecture,namely,[Cd^(Ⅱ)_(2)Cl_(2)(μ-Cl)_(2)(μ-L)]n[where L=1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane]was synthesized and structurally characterized.In this structure,the N4-coordinated pyrazole-based ligand displayed a chelating-bridging mode and bounds to two neighboring Cd^(Ⅱ)centers to create a 1D sinusoidal chain along the b-axis.Each of the cadmium(Ⅱ)sites adopted a distorted square pyramidal arrangement with a CdN_(2)Cl_(3)core.The chains were further stabilized by non-covalent bonds such as C-H⋯Cl and C-H⋯πto generate a 3D network.This structure has the ability to incorporate Fe_(3)O_(4)@SiO_(2)-NH_(2)nanoparticles and build up an Fe_(3)O_(4)@SiO_(2)-NH_(2)@Cd(Ⅱ)-CP hybrid using a sonochemical method.The bonding established between the Cd(Ⅱ)-CP and aminofunctionalized Fe_(3)O_(4)nanoparticles improved the separation of the CP by magnetic decantation.The products exhibited a high capacity and high selectivity to adsorb Congo red(CR)from an aqueous solution.The sorption kinetics and equilibrium isotherm were studied in detail using four kinetics and three isotherm models.According to the results that were obtained,the mechanism of the sorption process followed the pseudo-second-order kinetic and Langmuir isotherm models.In general,the magnetic hybrid under consideration can be proposed as a reversible catalyst for the selective adsorption of CR with facile separation from the environment using a magnetic bar.展开更多
文摘A sustainable four-step synthesis of soluble perylenophanes for applications as fluorescent optical functional materials is presented and even allows upscaling because of starting with technical bulk products. Thus, terminal alkenylnitriles were alkylated reduced to amines, condensed with perylenetetracarboxylic bisanhydride and cyclised to cyclophanes by means of double cross metathesis in yields until 69% of isolated dyes. The first metathesis by means of the second-generation Hoveyda-Grubbs-catalyst brings the remaining reactive olefinic groups close together favouring the ring-closure to the cyclophanes where the locked neighboring of chromophores in a skew arrangement induce strong exciton interactions. The latter cause an increased the Stokes’ separation by means of a moderate hypsochromic shift of light absorption and a stronger bathochromic shift of fluorescence. Various applications such as for lasers, photonics, solar collectors or in analytics are discussed.
基金Shahid Chamran University of Ahvaz for financial support(grant number:95/3/02/31579).
文摘A new non-covalently bonded 3D supramolecular architecture,namely,[Cd^(Ⅱ)_(2)Cl_(2)(μ-Cl)_(2)(μ-L)]n[where L=1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane]was synthesized and structurally characterized.In this structure,the N4-coordinated pyrazole-based ligand displayed a chelating-bridging mode and bounds to two neighboring Cd^(Ⅱ)centers to create a 1D sinusoidal chain along the b-axis.Each of the cadmium(Ⅱ)sites adopted a distorted square pyramidal arrangement with a CdN_(2)Cl_(3)core.The chains were further stabilized by non-covalent bonds such as C-H⋯Cl and C-H⋯πto generate a 3D network.This structure has the ability to incorporate Fe_(3)O_(4)@SiO_(2)-NH_(2)nanoparticles and build up an Fe_(3)O_(4)@SiO_(2)-NH_(2)@Cd(Ⅱ)-CP hybrid using a sonochemical method.The bonding established between the Cd(Ⅱ)-CP and aminofunctionalized Fe_(3)O_(4)nanoparticles improved the separation of the CP by magnetic decantation.The products exhibited a high capacity and high selectivity to adsorb Congo red(CR)from an aqueous solution.The sorption kinetics and equilibrium isotherm were studied in detail using four kinetics and three isotherm models.According to the results that were obtained,the mechanism of the sorption process followed the pseudo-second-order kinetic and Langmuir isotherm models.In general,the magnetic hybrid under consideration can be proposed as a reversible catalyst for the selective adsorption of CR with facile separation from the environment using a magnetic bar.
