Pagoda[5]arene(P5),which is composed of five 2,6-dimethoxylanthracene(2,6-DMA)subunits bridged by methylene groups at 1,5 positions,was conveniently synthesized in 43%by trifluoroacetic acid(TFA)-catalyzed one-pot con...Pagoda[5]arene(P5),which is composed of five 2,6-dimethoxylanthracene(2,6-DMA)subunits bridged by methylene groups at 1,5 positions,was conveniently synthesized in 43%by trifluoroacetic acid(TFA)-catalyzed one-pot condensation of commercially available 2,6-DMA and paraformaldehyde in 1,2-dichlorobenzene(o-DCB)at room temperature.P5 showed a highly symmetrical pentagonal structure with a large and deep electron-rich cavity,which made it form stable 1∶2 host–guest complexes with various aryl-pyridinium,bipyridinium,and stilbazolium salts in solution.Interestingly,P5 could complex two or even three guests with its intrinsic cavity and the pseudocavity formed by the adjacent macrocycles in solid states.Moreover,the strong intermolecular charge-transfer(ICT)interactions between P5 and the guests were observed.Especially,the complexes formed by P5 and the protonated pyridinium or bipyridinium salts showed acid/base-responsive color changes in solution and remarkable crystalline vapochromic properties by two kinds of processes:from ICT to no ICT and from ICT to enhanced ICT interaction or vice versa.We believe that the easily available P5 with the specific structure and intriguing 1∶2 host–guest complexation can find wide application in supramolecular assemblies and functional materials.展开更多
The synthesis,structure,and properties of pyrene-based conformationally adaptive macrocycles are described.This new type of conformationally adaptive macrocycle was constructed through Perkin reaction,followed by imid...The synthesis,structure,and properties of pyrene-based conformationally adaptive macrocycles are described.This new type of conformationally adaptive macrocycle was constructed through Perkin reaction,followed by imidization.By changing the condensation partner as the linking unit,a family of conjugated macrocycles with different sizes of the cavity was synthesized,which provide a simple and modular synthetic strategy towards the conformationally adaptive macrocycles.Furthermore,the macrocycles provide two well-defined conformations through flipping pyrene subunit,which were unambiguously determined by single-crystal X-ray diffraction analysis.The conformational interconversion barrier was determined by density functional theory(DFT)calculations.This new macrocycle also demonstrated unique properties,such as vapochromic behavior and aggregation emission enhancement effect.Furthermore,we have also investigated the effect of the linker on the shape and photophysical properties of the resulting macrocyclic products.展开更多
A new series of Ir(Ⅲ)carbene complexes with luminescent mechanochromism derived from trans-cis isomerization has been developed.Through the introduction of π-conjugating groups into the acyclic carbene ligand,the me...A new series of Ir(Ⅲ)carbene complexes with luminescent mechanochromism derived from trans-cis isomerization has been developed.Through the introduction of π-conjugating groups into the acyclic carbene ligand,the mechanochromic trans-and cisconfigurations can be readily interconverted,leading to dual emissive properties in the solid state.Moreover,the solid-or film-forming solvent system can control the dual emission and mechanoresponsive properties in the solid state.The potential uses of a single emissive complex to develop multicolor emissive and multiple stimuli-responsive films have been studied.展开更多
基金The authors thank the National Natural Science Foundation of China(nos.22031010,21772205,21521002,and 91856117)for financial support.
文摘Pagoda[5]arene(P5),which is composed of five 2,6-dimethoxylanthracene(2,6-DMA)subunits bridged by methylene groups at 1,5 positions,was conveniently synthesized in 43%by trifluoroacetic acid(TFA)-catalyzed one-pot condensation of commercially available 2,6-DMA and paraformaldehyde in 1,2-dichlorobenzene(o-DCB)at room temperature.P5 showed a highly symmetrical pentagonal structure with a large and deep electron-rich cavity,which made it form stable 1∶2 host–guest complexes with various aryl-pyridinium,bipyridinium,and stilbazolium salts in solution.Interestingly,P5 could complex two or even three guests with its intrinsic cavity and the pseudocavity formed by the adjacent macrocycles in solid states.Moreover,the strong intermolecular charge-transfer(ICT)interactions between P5 and the guests were observed.Especially,the complexes formed by P5 and the protonated pyridinium or bipyridinium salts showed acid/base-responsive color changes in solution and remarkable crystalline vapochromic properties by two kinds of processes:from ICT to no ICT and from ICT to enhanced ICT interaction or vice versa.We believe that the easily available P5 with the specific structure and intriguing 1∶2 host–guest complexation can find wide application in supramolecular assemblies and functional materials.
基金supported by the National Natural Science Foundation of China(Nos.21971041 and 22001039)Natural Science Foundation of Fujian Province(Nos.2018J01431,2018J01690 and 2020J01447)Research Foundation of Education Bureau of Fujian Province(No.JT180813)。
文摘The synthesis,structure,and properties of pyrene-based conformationally adaptive macrocycles are described.This new type of conformationally adaptive macrocycle was constructed through Perkin reaction,followed by imidization.By changing the condensation partner as the linking unit,a family of conjugated macrocycles with different sizes of the cavity was synthesized,which provide a simple and modular synthetic strategy towards the conformationally adaptive macrocycles.Furthermore,the macrocycles provide two well-defined conformations through flipping pyrene subunit,which were unambiguously determined by single-crystal X-ray diffraction analysis.The conformational interconversion barrier was determined by density functional theory(DFT)calculations.This new macrocycle also demonstrated unique properties,such as vapochromic behavior and aggregation emission enhancement effect.Furthermore,we have also investigated the effect of the linker on the shape and photophysical properties of the resulting macrocyclic products.
基金supported by the National Natural Science Foundation of China(22175181,92061202,and 21531008)Fujian Science and Technology Project(2020L3022)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)。
基金supported by the General Research Fund(Project No.CityU 11306819)from the Research Grants Council of the Hong Kong SAR,China.
文摘A new series of Ir(Ⅲ)carbene complexes with luminescent mechanochromism derived from trans-cis isomerization has been developed.Through the introduction of π-conjugating groups into the acyclic carbene ligand,the mechanochromic trans-and cisconfigurations can be readily interconverted,leading to dual emissive properties in the solid state.Moreover,the solid-or film-forming solvent system can control the dual emission and mechanoresponsive properties in the solid state.The potential uses of a single emissive complex to develop multicolor emissive and multiple stimuli-responsive films have been studied.
