Two isomorphous 2D zigzag-ladder structure coordination polymers containing coordination supramolecular capsules are reported,which are built by trivalent lanthanide ions,pyridine N-oxide（PNO） and p-sulfonatothiacal...Two isomorphous 2D zigzag-ladder structure coordination polymers containing coordination supramolecular capsules are reported,which are built by trivalent lanthanide ions,pyridine N-oxide（PNO） and p-sulfonatothiacalix[4]arene（H4TCAS4-）：[Ln2（PNO）2（H2O）10？（H2TCAS）2].[Ln2（H2TCAS）2（H2O）6（MeOH）2].2MeOH.12H2O（Ln = La,1;Nd,2）.Crystal data for complex 1：C31H51La2NO33S8,Mr = 1500.03,triclinic system,P 1 space group,with a = 11.732（2）,b = 15.007（3）,c = 15.262（3）,α = 78.05（3）,β = 80.77（3）,γ = 83.89（3）°,Z = 2,V = 2587.3（9）3,Dc = 1.925 g/cm3,μ = 2.051 mm-1,F（000） = 1500,the final R = 0.0300 and wR = 0.0823;and those for complex 2：C31H51Nd2NO33S8,Mr = 1510.69,triclinic system,P1 space group,with a = 11.719（2）,b = 14.941（3）,c = 15.157（3）,α = 78.03（3）,β = 80.84（3）,γ = 83.95（3）°,Z = 2,V = 2555.9（9）3,Dc = 1.963 g/cm3,μ = 2.436 mm-1,F（000） = 1512,the final R = 0.0493 and wR = 0.1267.There are two coordination environments of lanthanide ions.One is bridged by two PNO molecules forming a dimeric Ln ion in the O,O’-μ2 mode.The dinuclear ions are shrouded by two H2TCAS6-ions through coordination interactions and hydrogen bonds.The other coordination mode of Ln ions is a zigzag 1D chain linked by up-down H2TCAS6-ions.By the coordination capsules,the complexes form 2D zigzag-ladder structure coordination polymers.展开更多
Hydrogen-bonded capsules have been widely employed as supramolecular hosts for organic molecular guests.Encapsulation of fullerenes by capsules is relatively scarce,especially those that utilize sulfur atoms as hydrog...Hydrogen-bonded capsules have been widely employed as supramolecular hosts for organic molecular guests.Encapsulation of fullerenes by capsules is relatively scarce,especially those that utilize sulfur atoms as hydrogen-bond acceptors.Herein,we describe,in both solution and solid state,a bowl-shaped nanobelt[8]cyclophenoxathiin 1a and its tetra-methylated derivative 1b that can form C–H⋯S hydrogen-bonded capsules induced by complexation with suitable fullerenes.1a strongly encapsulates C60,C70,or 6,6-phenyl-C61-butyric acid methyl ester(PC61BM)to form a 2∶1 ternary complex featuring 16 equatorial(sp2)C–H⋯S hydrogen bonds.A pseudorotaxane structure was further obtained for the complex of 1a with PC61BM.Conversely,a 1∶1 inclusion complex was observed for binding C60 or PC61BM with 1b indicating the reduced tendency to form capsules by introducing methyl groups into the belt.Surprisingly,the capsule-like structure was retained for the 1:2 complex of C70 with 1b as observed by the presence of multiple(sp3)C–H⋯S hydrogen bonds.The strong binding affinity and tailorable complexation mode enable further applications of nanobelts in fullerene chemistry.展开更多
文摘Two isomorphous 2D zigzag-ladder structure coordination polymers containing coordination supramolecular capsules are reported,which are built by trivalent lanthanide ions,pyridine N-oxide（PNO） and p-sulfonatothiacalix[4]arene（H4TCAS4-）：[Ln2（PNO）2（H2O）10？（H2TCAS）2].[Ln2（H2TCAS）2（H2O）6（MeOH）2].2MeOH.12H2O（Ln = La,1;Nd,2）.Crystal data for complex 1：C31H51La2NO33S8,Mr = 1500.03,triclinic system,P 1 space group,with a = 11.732（2）,b = 15.007（3）,c = 15.262（3）,α = 78.05（3）,β = 80.77（3）,γ = 83.89（3）°,Z = 2,V = 2587.3（9）3,Dc = 1.925 g/cm3,μ = 2.051 mm-1,F（000） = 1500,the final R = 0.0300 and wR = 0.0823;and those for complex 2：C31H51Nd2NO33S8,Mr = 1510.69,triclinic system,P1 space group,with a = 11.719（2）,b = 14.941（3）,c = 15.157（3）,α = 78.03（3）,β = 80.84（3）,γ = 83.95（3）°,Z = 2,V = 2555.9（9）3,Dc = 1.963 g/cm3,μ = 2.436 mm-1,F（000） = 1512,the final R = 0.0493 and wR = 0.1267.There are two coordination environments of lanthanide ions.One is bridged by two PNO molecules forming a dimeric Ln ion in the O,O’-μ2 mode.The dinuclear ions are shrouded by two H2TCAS6-ions through coordination interactions and hydrogen bonds.The other coordination mode of Ln ions is a zigzag 1D chain linked by up-down H2TCAS6-ions.By the coordination capsules,the complexes form 2D zigzag-ladder structure coordination polymers.
基金the National Natural Science Foundation of China(grant nos.21971268 and 22171295)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(grant no.2017ZT07C069)+1 种基金Pearl River Talent Program(grant no.2017GC010623)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(grant no.SN-ZJU-SIAS-006)for financial support.
文摘Hydrogen-bonded capsules have been widely employed as supramolecular hosts for organic molecular guests.Encapsulation of fullerenes by capsules is relatively scarce,especially those that utilize sulfur atoms as hydrogen-bond acceptors.Herein,we describe,in both solution and solid state,a bowl-shaped nanobelt[8]cyclophenoxathiin 1a and its tetra-methylated derivative 1b that can form C–H⋯S hydrogen-bonded capsules induced by complexation with suitable fullerenes.1a strongly encapsulates C60,C70,or 6,6-phenyl-C61-butyric acid methyl ester(PC61BM)to form a 2∶1 ternary complex featuring 16 equatorial(sp2)C–H⋯S hydrogen bonds.A pseudorotaxane structure was further obtained for the complex of 1a with PC61BM.Conversely,a 1∶1 inclusion complex was observed for binding C60 or PC61BM with 1b indicating the reduced tendency to form capsules by introducing methyl groups into the belt.Surprisingly,the capsule-like structure was retained for the 1:2 complex of C70 with 1b as observed by the presence of multiple(sp3)C–H⋯S hydrogen bonds.The strong binding affinity and tailorable complexation mode enable further applications of nanobelts in fullerene chemistry.
