Self-assembly of a functional cryptand core（1） having six dithiocarbamate groups and \{（dppm）Au2Cl\}2 in methanol followed by the addition of excess NH4PF6 affords a novel metallodendritic supramolecule（2）. This...Self-assembly of a functional cryptand core（1） having six dithiocarbamate groups and \{（dppm）Au2Cl\}2 in methanol followed by the addition of excess NH4PF6 affords a novel metallodendritic supramolecule（2）. This dendritic supramolecule was characterized by NMR, MS, XPS, IR, UV-Vis, luminescence spectra and elemental analyses. The results show the concentration-dependent absorption and luminescent properties in acetonitrile solution for the title compound, which may be closely related to the intramolecular and intermolecular aggregation of digold（Ⅰ） branches through Au（Ⅰ）…Au（Ⅰ） interactions.展开更多
A new method for the preparation of a soluble ladderlike polymethylsilsesquioxane with high molecular weight ((?)=10~5—10~6) and low molecular weight distribution (D=Mw/Mn) in common solvents instead of the formerly ...A new method for the preparation of a soluble ladderlike polymethylsilsesquioxane with high molecular weight ((?)=10~5—10~6) and low molecular weight distribution (D=Mw/Mn) in common solvents instead of the formerly used toxic methylisobutylketone has been developed. The structure and macromolecular regularity were characterized by IR, X-ray diffraction, and ^(29)Si-NMR spectroscopy. The thermal property was studied by TGA and DSC.展开更多
The high molecular ladderlike polyhydrosilsesquioxane （LPHSQ） and its copolymer, ladderlike random copolymethylhydrosilsesquioxane （LR-PMHSQ） and ladderlike block copolymethylsilsesqui-oxane（LB-PMHSQ） have been ...The high molecular ladderlike polyhydrosilsesquioxane （LPHSQ） and its copolymer, ladderlike random copolymethylhydrosilsesquioxane （LR-PMHSQ） and ladderlike block copolymethylsilsesqui-oxane（LB-PMHSQ） have been synthesized by a preaminolysis reaction of the corresponding trichlorosilane with 1 ,4-phenylene diamine（PDA） then by hydrolysis and polycondensation reactions The thermographs of these polymers measured by DSC method indicate that these macromolecular backbones are very rigid as seen from the DSC curves which are almost horizontal from room temperature until 350;without noticeable glass transition. The content of Si—H group in the polymers can be regulated by changing the composition of the two copolymerized monomers. So the ladderlike polymers including its copolymers can be the useful precursors for the functional polymers, especially such as fishbone-like liquid crystalline polymers.展开更多
Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preammi...Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preamminolysis, hydrolysis and polycondensation reactions. The preparation method can be carried out easily at the temperature below 95℃ with high yield of 95 %, instead of the conventional way by using high-boiling solvent and any reaction activator or by precipitation with methanol. Three kinds of ladderlike polymers have been characterized. The MW's of the polymers reached to 10~6 without noticeable gelling. The scheme for synthetic route has been proposed.展开更多
A novel ordered reactive oligomeric ladderlike copolymethyl-aminopropylsilsesquioxane(Me-AP-T),was successfully synthesized by an efficient hydrosilylation graft reaction of 1,1,1-trimethyl-N-2-propenyl-silanamine wit...A novel ordered reactive oligomeric ladderlike copolymethyl-aminopropylsilsesquioxane(Me-AP-T),was successfully synthesized by an efficient hydrosilylation graft reaction of 1,1,1-trimethyl-N-2-propenyl-silanamine with a reactive oligomeric ladderlike copolymethyl-hydrosilsesquioxane(Me-H-T),which was prepared by“supramolecular chemistry-dictated stepwise coupling polymerization”process.FT-IR,~1H-and ^(29)Si-NMR spectra show that hydrosilylation reaction proceeds completely.Moreover,~1H-NMR spectra also indicate that both the molar ratios of≡SiMe group to Si—H and≡SiMe group to≡SiPrNH_2 are approximately 1:1 respectively based on the ratio of integrated resonance areas of the different groups.XRD analysis and ^(29)Si-NMR spectra are used for investigating the ladderlike structure of the polymers.A high T_g(128.38℃)of Me-AP-T shown in DSC measurement implies that the ordered reactive Me-AP-T macromolecules have much stiff chains.展开更多
Fluorescent molecules - p-dimethylaminobenzonitrile (DMABN) and trans-stilbene (TSB ) - were used as probes to investigate the inner structure of the nanotubular cavities contained in a new polyorganosiloxane (POS) wh...Fluorescent molecules - p-dimethylaminobenzonitrile (DMABN) and trans-stilbene (TSB ) - were used as probes to investigate the inner structure of the nanotubular cavities contained in a new polyorganosiloxane (POS) which was prepared by the hydrosilylation coupling reaction of cis-isotactic ladderlike polyvinylsilsesquioxane (Vi-T) with 1,1,3,3-tetramethyldisiloxane (H-MM) as coupling agent in the presence of catalyst dicyclopentadienyldichloroplatinum (Cp2PtCl2). The results from FTIR spectra and fluorescence spectra in combination with molecular simulation reveal that the cross-section of the nanotubular cavity is nearly rectangular in shape, and is about 0.62 nm in width and about 0.38 nm in height. This work gains in-depth knowledge into the inner structure of the nanotubular cavities of POS and furthermore provides a guide to the selection of proper guest molecules in constructing functional supramolecular clathrate based upon POS.展开更多
文摘Self-assembly of a functional cryptand core（1） having six dithiocarbamate groups and \{（dppm）Au2Cl\}2 in methanol followed by the addition of excess NH4PF6 affords a novel metallodendritic supramolecule（2）. This dendritic supramolecule was characterized by NMR, MS, XPS, IR, UV-Vis, luminescence spectra and elemental analyses. The results show the concentration-dependent absorption and luminescent properties in acetonitrile solution for the title compound, which may be closely related to the intramolecular and intermolecular aggregation of digold（Ⅰ） branches through Au（Ⅰ）…Au（Ⅰ） interactions.
文摘A new method for the preparation of a soluble ladderlike polymethylsilsesquioxane with high molecular weight ((?)=10~5—10~6) and low molecular weight distribution (D=Mw/Mn) in common solvents instead of the formerly used toxic methylisobutylketone has been developed. The structure and macromolecular regularity were characterized by IR, X-ray diffraction, and ^(29)Si-NMR spectroscopy. The thermal property was studied by TGA and DSC.
基金This project was supported by Beijing National Laboratory of Structural Chemistry of Stable and Unstable Species.
文摘The high molecular ladderlike polyhydrosilsesquioxane （LPHSQ） and its copolymer, ladderlike random copolymethylhydrosilsesquioxane （LR-PMHSQ） and ladderlike block copolymethylsilsesqui-oxane（LB-PMHSQ） have been synthesized by a preaminolysis reaction of the corresponding trichlorosilane with 1 ,4-phenylene diamine（PDA） then by hydrolysis and polycondensation reactions The thermographs of these polymers measured by DSC method indicate that these macromolecular backbones are very rigid as seen from the DSC curves which are almost horizontal from room temperature until 350;without noticeable glass transition. The content of Si—H group in the polymers can be regulated by changing the composition of the two copolymerized monomers. So the ladderlike polymers including its copolymers can be the useful precursors for the functional polymers, especially such as fishbone-like liquid crystalline polymers.
基金supported by the National Natural Science Foundation of China(Nos.20174047,20204016,50273043,29974036,50073028)the Doctor Research Foundation of Zhengzhou University of Light Industry(No.000310)
文摘Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preamminolysis, hydrolysis and polycondensation reactions. The preparation method can be carried out easily at the temperature below 95℃ with high yield of 95 %, instead of the conventional way by using high-boiling solvent and any reaction activator or by precipitation with methanol. Three kinds of ladderlike polymers have been characterized. The MW's of the polymers reached to 10~6 without noticeable gelling. The scheme for synthetic route has been proposed.
基金This work was supported by the National Natural Science Foundation of China(Nos.50273043,20204016,20174047)
文摘A novel ordered reactive oligomeric ladderlike copolymethyl-aminopropylsilsesquioxane(Me-AP-T),was successfully synthesized by an efficient hydrosilylation graft reaction of 1,1,1-trimethyl-N-2-propenyl-silanamine with a reactive oligomeric ladderlike copolymethyl-hydrosilsesquioxane(Me-H-T),which was prepared by“supramolecular chemistry-dictated stepwise coupling polymerization”process.FT-IR,~1H-and ^(29)Si-NMR spectra show that hydrosilylation reaction proceeds completely.Moreover,~1H-NMR spectra also indicate that both the molar ratios of≡SiMe group to Si—H and≡SiMe group to≡SiPrNH_2 are approximately 1:1 respectively based on the ratio of integrated resonance areas of the different groups.XRD analysis and ^(29)Si-NMR spectra are used for investigating the ladderlike structure of the polymers.A high T_g(128.38℃)of Me-AP-T shown in DSC measurement implies that the ordered reactive Me-AP-T macromolecules have much stiff chains.
基金This project was co-funded by National Natural Science Foundation of China,Research Foundation of Molecular Science Centre and Director of Institute of Chemistry,Chinese Academy of Sciences and Foundation of Organic Solid Laboratory,Chinese Academy of Sc
文摘Fluorescent molecules - p-dimethylaminobenzonitrile (DMABN) and trans-stilbene (TSB ) - were used as probes to investigate the inner structure of the nanotubular cavities contained in a new polyorganosiloxane (POS) which was prepared by the hydrosilylation coupling reaction of cis-isotactic ladderlike polyvinylsilsesquioxane (Vi-T) with 1,1,3,3-tetramethyldisiloxane (H-MM) as coupling agent in the presence of catalyst dicyclopentadienyldichloroplatinum (Cp2PtCl2). The results from FTIR spectra and fluorescence spectra in combination with molecular simulation reveal that the cross-section of the nanotubular cavity is nearly rectangular in shape, and is about 0.62 nm in width and about 0.38 nm in height. This work gains in-depth knowledge into the inner structure of the nanotubular cavities of POS and furthermore provides a guide to the selection of proper guest molecules in constructing functional supramolecular clathrate based upon POS.
