The monomer 2,6,12-triaminotriptycene was synthesized and the structure was confirmed by IR and 1H NMR spectra. Hyperbranched polyimides modified with different terminal groups were obtained from precursors, anhydride...The monomer 2,6,12-triaminotriptycene was synthesized and the structure was confirmed by IR and 1H NMR spectra. Hyperbranched polyimides modified with different terminal groups were obtained from precursors, anhydride- and aminoterminated hyperbranched poly（amic acid）s from polymerization of A2 ＋ B3 system. From gel permeation chromatograrn （GPC） characterization, representative products had high molecular weight. All polymers had good solubility in CHCl3, DMF and tetrahydrofuran （THF）, and performed no detective Tgs in the range of 50-300 ℃ and high Tds above 455 ℃ when 5% weight loss.展开更多
Single crystals of two triptycene-based catechol derivatives 1 and 2 were obtained,and their X-ray crystal structural studies showed that the two tecton molecules had different conformations in the solid state,and the...Single crystals of two triptycene-based catechol derivatives 1 and 2 were obtained,and their X-ray crystal structural studies showed that the two tecton molecules had different conformations in the solid state,and they could self-assemble into interesting 3D networks with solvent molecules included inside, in which multiple O-H…O hydrogen bonds played important roles.展开更多
A break junction technique has been established to explore conductive behavior at the single molecular level,and recent interest has shifted toward the evaluation of bimolecular systems interacting through noncovalent...A break junction technique has been established to explore conductive behavior at the single molecular level,and recent interest has shifted toward the evaluation of bimolecular systems interacting through noncovalent intermolecular forces.This requires precise control over the orientation of the two molecules so that they can adapt an appropriate face-to-face arrangement between two electrodes.Herein,we present an approach using a tripodal triptycene scaffold that allows for accurate positioning of electroactive subunits with an upright configuration on substrate surfaces.We incorporated electron-donating tetrathiafulvalene or electron-accepting anthraquinone into the molecular scaffold and confirmed that the resulting molecules retain the electronic properties particular to their attached subunits.Self-assembled monolayers(SAMs)of these molecules were prepared on Au(111)and characterized by XPS and STM.STM break junction techniques were applied to the SAMs,revealing two electrical conduction regimes;one arises from single-molecules sandwiched between two electrodes,and the second from intermolecularly interacting homodimers that bridge between electrodes.This observation demonstrates the validity of the approach of using tripodal triptycene scaffolds to precisely direct electroactive subunits to undergo intermolecular pairing.We believe that the present work will provide a new avenue for evaluating the heterodimers at the single molecular level.展开更多
A novel triptycene-based dianhyride as a shape-persistent building block with high internal free volume was conveniently synthesized via solvothermal method.Subsequently,three all-aromatic polyimides,Pla,PIb and PIc,w...A novel triptycene-based dianhyride as a shape-persistent building block with high internal free volume was conveniently synthesized via solvothermal method.Subsequently,three all-aromatic polyimides,Pla,PIb and PIc,were prepared by a one-step polycondensation of triptycene-2,3,6,7-tetracarboxylic dianhydride with 2,2＇-bis（trifluoromethyl）benzidine,m-tolidine and 3,3＇,5,5＇-tetramethylbenzidine,respectively.The corresponding polymers exhibit good solubility,excellent thermal stability,significant microporosity with large BET surface areas of up to 623 m^-2 g^-1 as well as an unexpected optical property with a transmittance of -85%at 450 nm as -20μm membranes.展开更多
In this report we investigated two-dimensionally triptycene end-capped QPPs in terms of their solution and solid-state behavior.For this purpose,a triphenylene based ortho-diamine decorated with two triptycenyl units ...In this report we investigated two-dimensionally triptycene end-capped QPPs in terms of their solution and solid-state behavior.For this purpose,a triphenylene based ortho-diamine decorated with two triptycenyl units as well as a phenylene diamine with two non-annulated triptycene units have been synthesized.Sequences of condensation reactions with a pyrene-based tetraketone and ortho-diamines yielded a series of QPPs and UV/Vis investigations of the corresponding compounds led to the conclusion,that the QPPs form dimers in solution,which was further supported by MALDI-TIMS-TOF-MS.Single-crystal X-ray analysis of the triply and quadruply triptycene end-capped QPPs furthermore showed shortπ-π-distances of 3.3-3.4?and a perfect shape match during the dimerization of the triply triptycenyl end-capped QPP making it possible synthon for crystal engineering.展开更多
Based on monomer 2,6,12-triaminotriptycene, hyperbranched polyimides with high molecular weight modified with different terminal functional groups were obtained by polymerization of A2 ＋ B3 system. The prepared hyper...Based on monomer 2,6,12-triaminotriptycene, hyperbranched polyimides with high molecular weight modified with different terminal functional groups were obtained by polymerization of A2 ＋ B3 system. The prepared hyperbranched polyimides had good solubility in CHCl3, DMF and THF, and performed no detective Tgs in the range of 50-330℃ and high TdS （5%） above 455℃.展开更多
A rapid and efficient synthesis of novel dendrimer homotriptycenes is presented. The dendronized 9,10-dihydroanthracen-9-ols 4, having high electron densities in the benzene rings of the Fréchet-type dendrons, ex...A rapid and efficient synthesis of novel dendrimer homotriptycenes is presented. The dendronized 9,10-dihydroanthracen-9-ols 4, having high electron densities in the benzene rings of the Fréchet-type dendrons, exhibited in the presence of acid a quantitative transannular ring closure to the corresponding dendritic homotriptycenes. The electron-donating Fréchet-type dendrons enabled the intramolecular FC alkylation by a regioselective 1,7-elimination of H2O.展开更多
Triptycene-derived cylindrical macrotricyclic host with two dibenzo-30-crown-lO cavities could form stable 1 ： 1 complexes with not only polyether linked bisparaquat derivative but also a self-folding A-D-A guest in ...Triptycene-derived cylindrical macrotricyclic host with two dibenzo-30-crown-lO cavities could form stable 1 ： 1 complexes with not only polyether linked bisparaquat derivative but also a self-folding A-D-A guest in solu- tion and/or solid state. Moreover, it was found that switchable processes between the host and both the bisparaquat derivative and the self-folding guest could be further controlled by potassium ions.展开更多
A series of triptycene-derived Tr6ger＇s bases with molecular clip shaped structures have been conveniently and efficiently synthesized by one-pot condensation of corresponding amino-substituted triptycenes with paraf...A series of triptycene-derived Tr6ger＇s bases with molecular clip shaped structures have been conveniently and efficiently synthesized by one-pot condensation of corresponding amino-substituted triptycenes with paraformaldehyde in the presence of trifluoroacetic acid, and their structures have been characterized by NMR, MALDI-TOF MS spectra, elemental analyses and single-crystal X-ray diffraction. ~ 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.展开更多
基金the National Natural Science Foundation(No.50673031)of China and authors would like to extend thanks to Professor Yongming Chen at CAS.
文摘The monomer 2,6,12-triaminotriptycene was synthesized and the structure was confirmed by IR and 1H NMR spectra. Hyperbranched polyimides modified with different terminal groups were obtained from precursors, anhydride- and aminoterminated hyperbranched poly（amic acid）s from polymerization of A2 ＋ B3 system. From gel permeation chromatograrn （GPC） characterization, representative products had high molecular weight. All polymers had good solubility in CHCl3, DMF and tetrahydrofuran （THF）, and performed no detective Tgs in the range of 50-300 ℃ and high Tds above 455 ℃ when 5% weight loss.
基金the National Natural Science Foundation of China (Nos.91127009,20972162)the National Basic Research Program(No.2011CB932501) for financial support
文摘Single crystals of two triptycene-based catechol derivatives 1 and 2 were obtained,and their X-ray crystal structural studies showed that the two tecton molecules had different conformations in the solid state,and they could self-assemble into interesting 3D networks with solvent molecules included inside, in which multiple O-H…O hydrogen bonds played important roles.
基金JSPS KAKENHI(JP21H05024,JP21H04690,and JP20H05868 for Ta.F.and Japan Science and Technology Agency(JST)CREST(JPMJCR18I4)for Ta.F.This work was also supported in part by the Research Program of“Five-Star Alliance”in“NJRC Mater.&Dev.”.
文摘A break junction technique has been established to explore conductive behavior at the single molecular level,and recent interest has shifted toward the evaluation of bimolecular systems interacting through noncovalent intermolecular forces.This requires precise control over the orientation of the two molecules so that they can adapt an appropriate face-to-face arrangement between two electrodes.Herein,we present an approach using a tripodal triptycene scaffold that allows for accurate positioning of electroactive subunits with an upright configuration on substrate surfaces.We incorporated electron-donating tetrathiafulvalene or electron-accepting anthraquinone into the molecular scaffold and confirmed that the resulting molecules retain the electronic properties particular to their attached subunits.Self-assembled monolayers(SAMs)of these molecules were prepared on Au(111)and characterized by XPS and STM.STM break junction techniques were applied to the SAMs,revealing two electrical conduction regimes;one arises from single-molecules sandwiched between two electrodes,and the second from intermolecularly interacting homodimers that bridge between electrodes.This observation demonstrates the validity of the approach of using tripodal triptycene scaffolds to precisely direct electroactive subunits to undergo intermolecular pairing.We believe that the present work will provide a new avenue for evaluating the heterodimers at the single molecular level.
基金the National Natural Science Foundation of China(No.51473055)for financial support
文摘A novel triptycene-based dianhyride as a shape-persistent building block with high internal free volume was conveniently synthesized via solvothermal method.Subsequently,three all-aromatic polyimides,Pla,PIb and PIc,were prepared by a one-step polycondensation of triptycene-2,3,6,7-tetracarboxylic dianhydride with 2,2＇-bis（trifluoromethyl）benzidine,m-tolidine and 3,3＇,5,5＇-tetramethylbenzidine,respectively.The corresponding polymers exhibit good solubility,excellent thermal stability,significant microporosity with large BET surface areas of up to 623 m^-2 g^-1 as well as an unexpected optical property with a transmittance of -85%at 450 nm as -20μm membranes.
基金grateful to"Deutsche Forschungsgemeinschaft"supporting this project(SFB1249"N-heteropolycyclic compounds as functional materials"TP-A04).support by the state of Baden-Wurttemberg through bwHPC and the German Research Foundation(DFG)through grant no.INST 40/575-1 FUGG(JUSTUS 2 cluster).
文摘In this report we investigated two-dimensionally triptycene end-capped QPPs in terms of their solution and solid-state behavior.For this purpose,a triphenylene based ortho-diamine decorated with two triptycenyl units as well as a phenylene diamine with two non-annulated triptycene units have been synthesized.Sequences of condensation reactions with a pyrene-based tetraketone and ortho-diamines yielded a series of QPPs and UV/Vis investigations of the corresponding compounds led to the conclusion,that the QPPs form dimers in solution,which was further supported by MALDI-TIMS-TOF-MS.Single-crystal X-ray analysis of the triply and quadruply triptycene end-capped QPPs furthermore showed shortπ-π-distances of 3.3-3.4?and a perfect shape match during the dimerization of the triply triptycenyl end-capped QPP making it possible synthon for crystal engineering.
基金supported by the National Natural Science Foundation of China(Nos.50673031 and 50973036)the Natural Science Foundation of Fujian Province(No.2008F3067)
文摘Based on monomer 2,6,12-triaminotriptycene, hyperbranched polyimides with high molecular weight modified with different terminal functional groups were obtained by polymerization of A2 ＋ B3 system. The prepared hyperbranched polyimides had good solubility in CHCl3, DMF and THF, and performed no detective Tgs in the range of 50-330℃ and high TdS （5%） above 455℃.
基金Supported by the National Natural Science Foundation of China (Grant Nos.20572111 & 20872038)the Science and Technology Planning Project of Guang-dong Province, China (Grant No.2007A010500011)the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20060561024)
文摘A rapid and efficient synthesis of novel dendrimer homotriptycenes is presented. The dendronized 9,10-dihydroanthracen-9-ols 4, having high electron densities in the benzene rings of the Fréchet-type dendrons, exhibited in the presence of acid a quantitative transannular ring closure to the corresponding dendritic homotriptycenes. The electron-donating Fréchet-type dendrons enabled the intramolecular FC alkylation by a regioselective 1,7-elimination of H2O.
基金We thank the National Natural Science Foundation of China，the National Basic Research Program (No.2011CB932501) for financial support
文摘Triptycene-derived cylindrical macrotricyclic host with two dibenzo-30-crown-lO cavities could form stable 1 ： 1 complexes with not only polyether linked bisparaquat derivative but also a self-folding A-D-A guest in solu- tion and/or solid state. Moreover, it was found that switchable processes between the host and both the bisparaquat derivative and the self-folding guest could be further controlled by potassium ions.
基金the National Natural Science Foundation of China (Nos. 21332008, 51373180)the National Basic Research Program (No. 2011CB932501) for financial support
文摘A series of triptycene-derived Tr6ger＇s bases with molecular clip shaped structures have been conveniently and efficiently synthesized by one-pot condensation of corresponding amino-substituted triptycenes with paraformaldehyde in the presence of trifluoroacetic acid, and their structures have been characterized by NMR, MALDI-TOF MS spectra, elemental analyses and single-crystal X-ray diffraction. ~ 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
