Three novel C2-symmetric macrocycles containing pyridyl units have been prepared by the cyclic condensation of chiral diamide intermediates with 2,6-pyridinedicarbonyl dichloride in highly diluted solution at room tem...Three novel C2-symmetric macrocycles containing pyridyl units have been prepared by the cyclic condensation of chiral diamide intermediates with 2,6-pyridinedicarbonyl dichloride in highly diluted solution at room temperature.展开更多
Trifluoroacetic acid(TFA)catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH_(2)Cl2afforded a single product in 87%–89%yield.Well-defined yet undissolvable...Trifluoroacetic acid(TFA)catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH_(2)Cl2afforded a single product in 87%–89%yield.Well-defined yet undissolvable1H NMR spectra suggested formation of robust and discrete structures in solution.X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state,which was formed from[4+8]condensation of the two reactants via 16 imine bonds.DFT calculations discovered that only the[4+8]twisted product is thermodynamically favorable,which accounts for its highly selective and efficient formation out of a library of many other combinations.展开更多
Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved...Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved in catalysis,sensing,and chiroptical switching.However,the synthesis of enantiopure supramolecular entities with crystallographic structures remains challenging.Herein,the stereoselective self-assembly of chiral metalla[2]catenanes interlocked by two D-shaped macrocycles was realized by combining long binuclear half-sandwich organometallic Cp*Rh^(III)(Cp*=η^(5)-pentamethylcyclopentadienyl)clip and ditopic monodentate ligand incorporating L-leucine residues.The resulting metalla[2]catenane displayed unique co-conformational mechanical helical chirality characteristics arising from the chirality transfer of the chiral ligand.Furthermore,decreasing the length of the binuclear Cp*Rh^(III)clip and adjusting the steric hindrance of the amino-acid side chains(L-alanine and L-phenylalanine)in the ligands resulted in two lemniscular macrocycles with left-handed(M)-twisted conformational chirality.To the best of our knowledge,the synthesized macrocycles are the first family of homochiral abnormal lemniscate-shaped organometallic macrocycles featuring figure-eight geometries.Metalla[2]catenanes and macrocycles with opposite chirality were also generated by employing corresponding D-amino acid ligands,as evidenced by single-crystal X-ray diffraction,nuclear magnetic resonance,mass,and circular dichroism spectroscopies.Our present study demonstrates that homochiral MIMs can be accessed readily using amino acid–containing ligands through rational molecular design.展开更多
The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]...The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]（ClO4）2（1） and [Ni（SS-L）（β-l-HPhe）]（ClO4）2（2）, respectively（L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine）. Single-crystal X-ray diffraction analyses revealed that the nickel（Ⅱ） atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni（RR-L）（β-d-HPhe）]2＋ and [Ni（SS-L）（β-l-HPhe）]2＋ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.展开更多
In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff...In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.展开更多
In the present work,two Troger's base-based macrocycles(TBBMs)with different bridging ethylene glycol chains(T1,n=1;T3,n=3)were successfully synthesized and studied via the crystal analysis.These two TBBMs possess...In the present work,two Troger's base-based macrocycles(TBBMs)with different bridging ethylene glycol chains(T1,n=1;T3,n=3)were successfully synthesized and studied via the crystal analysis.These two TBBMs possess rare rectangular-like cavities and show chiral selection during the crystallization.T1with short glycol chain(n=1)crystallized as racemates,while T3 with long glycol chain(n=3)was found as meso isomer.In contrast to T1 and T3,for T2(n=2)both rac-T2 and meso isomer R2NS2N-T2has been observed in our previous report.Thus,the synthesis of new TBBMs T1 and T3 with different bridging ethylene glycol chains not only makes the study of TBBMs more systematically,but also helps to understand the relationship between the size of the rectangular cavity and the chiral selection of Troger's base-based macrocycles during their crystallization.展开更多
A novel good water-soluble macrocycle containing two pyridinium moieties was synthesized in high yield.It could form 1:1 complexes with neutral guests containing naphthalene or phenyl units in water.The water-soluble ...A novel good water-soluble macrocycle containing two pyridinium moieties was synthesized in high yield.It could form 1:1 complexes with neutral guests containing naphthalene or phenyl units in water.The water-soluble macrocycle can selectively encapsulate naphthalene to form a 1:1 complex over a variety of polycyclic aromatic hydrocarbons.展开更多
An efficient strategy for constructing chiral macrocycles with both thermally activated delayed fluorescence(TADF)and highly efficient circularly polarized electroluminescence(CPEL)properties was developed.Consequentl...An efficient strategy for constructing chiral macrocycles with both thermally activated delayed fluorescence(TADF)and highly efficient circularly polarized electroluminescence(CPEL)properties was developed.Consequently,a pair of macrocyclic enantiomers(+)-(R,R)-MC and(−)-(S,S)-MC was synthesized by a combination of chiral octahydro-binaphthol moiety with triazine-based TADF skeleton.The chiral macrocycles exhibited obvious TADF properties with a lowΔE_(ST) of 0.067 eV,aggregation-induced emission behaviors,and high photoluminescence quantum yields of up to 79.7%.Moreover,the macrocyclic enantiomers showed mirror images in circular dichroism spectra and circularly polarized luminescence signals.Especially,the chiralmacrocycleswere suitable for the preparation of solution-processed circularly polarized organic light-emitting diodes,which displayed excellent device performances with a highmaximum external quantum efficiency of up to 17.1%,low-efficiency roll-off of 3.5%at 1000 cdm^(−2),andintenseCPELalong with electroluminescence dissymmetry factor of 1.7×10^(−3).展开更多
以R-联萘酚、氯氰胺、间苯二胺、1,2二苯基乙二胺、乙二胺为原料合成了3个水溶性手性大环荧光传感器;利用核磁共振(1 H NMR和13 C NMR)、质谱、红外光谱验证了合成产物的结构,利用元素分析仪测定了其组成,并利用X射线衍射分析确定了单晶...以R-联萘酚、氯氰胺、间苯二胺、1,2二苯基乙二胺、乙二胺为原料合成了3个水溶性手性大环荧光传感器;利用核磁共振(1 H NMR和13 C NMR)、质谱、红外光谱验证了合成产物的结构,利用元素分析仪测定了其组成,并利用X射线衍射分析确定了单晶R-3的晶体结构.结果表明,R-3属于单斜晶系,P2(1)/n空间群,晶胞参数为:a=1.128 6nm,b=1.566 1nm,c=2.293 9nm,β=90°,Z=4,Dc=1.328g.cm-3,F(000)=1 684.展开更多
文摘Three novel C2-symmetric macrocycles containing pyridyl units have been prepared by the cyclic condensation of chiral diamide intermediates with 2,6-pyridinedicarbonyl dichloride in highly diluted solution at room temperature.
基金supported by the National Natural Science Foundation of China(Nos.21971223 and 21772178)。
文摘Trifluoroacetic acid(TFA)catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH_(2)Cl2afforded a single product in 87%–89%yield.Well-defined yet undissolvable1H NMR spectra suggested formation of robust and discrete structures in solution.X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state,which was formed from[4+8]condensation of the two reactants via 16 imine bonds.DFT calculations discovered that only the[4+8]twisted product is thermodynamically favorable,which accounts for its highly selective and efficient formation out of a library of many other combinations.
基金the National Science Foundation of China(grant nos.22031003 and 21720102004)the Shanghai Science Technology Committee,China(grant no.19DZ2270100)the Shanghai Post-doctoral Excellence Program,China(grant no.2022009).
文摘Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved in catalysis,sensing,and chiroptical switching.However,the synthesis of enantiopure supramolecular entities with crystallographic structures remains challenging.Herein,the stereoselective self-assembly of chiral metalla[2]catenanes interlocked by two D-shaped macrocycles was realized by combining long binuclear half-sandwich organometallic Cp*Rh^(III)(Cp*=η^(5)-pentamethylcyclopentadienyl)clip and ditopic monodentate ligand incorporating L-leucine residues.The resulting metalla[2]catenane displayed unique co-conformational mechanical helical chirality characteristics arising from the chirality transfer of the chiral ligand.Furthermore,decreasing the length of the binuclear Cp*Rh^(III)clip and adjusting the steric hindrance of the amino-acid side chains(L-alanine and L-phenylalanine)in the ligands resulted in two lemniscular macrocycles with left-handed(M)-twisted conformational chirality.To the best of our knowledge,the synthesized macrocycles are the first family of homochiral abnormal lemniscate-shaped organometallic macrocycles featuring figure-eight geometries.Metalla[2]catenanes and macrocycles with opposite chirality were also generated by employing corresponding D-amino acid ligands,as evidenced by single-crystal X-ray diffraction,nuclear magnetic resonance,mass,and circular dichroism spectroscopies.Our present study demonstrates that homochiral MIMs can be accessed readily using amino acid–containing ligands through rational molecular design.
基金Supported by the Scientific Research Fund of Hunan Provincial Education Department(13B029,13A030,13CY029)the Program for Excellent Talents in Hunan University of Science and Engineering(2013)+2 种基金the Construct Program of the Key Discipline in Hunan Province(2011-76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province(2012-318)NSF of Hunan(11JJ2009)
文摘The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]（ClO4）2（1） and [Ni（SS-L）（β-l-HPhe）]（ClO4）2（2）, respectively（L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine）. Single-crystal X-ray diffraction analyses revealed that the nickel（Ⅱ） atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni（RR-L）（β-d-HPhe）]2＋ and [Ni（SS-L）（β-l-HPhe）]2＋ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.
基金Xunta de Galicia for his postdoctoral fellowship(ED481B-2022-068)the Fundación Segundo Gil Dávila for her PhD fellowship。
文摘In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.
基金the financial support from the National Natural Science Foundation of China(Nos.21901113,21871135)the Natural Science Foundation of Jiangsu Province(No.BK20190287)financially supported by the Starry Night Science Foundation of Zhejiang University Shanghai Institute for Advanced Study(No.SN-ZJU-SIAS-006)。
文摘In the present work,two Troger's base-based macrocycles(TBBMs)with different bridging ethylene glycol chains(T1,n=1;T3,n=3)were successfully synthesized and studied via the crystal analysis.These two TBBMs possess rare rectangular-like cavities and show chiral selection during the crystallization.T1with short glycol chain(n=1)crystallized as racemates,while T3 with long glycol chain(n=3)was found as meso isomer.In contrast to T1 and T3,for T2(n=2)both rac-T2 and meso isomer R2NS2N-T2has been observed in our previous report.Thus,the synthesis of new TBBMs T1 and T3 with different bridging ethylene glycol chains not only makes the study of TBBMs more systematically,but also helps to understand the relationship between the size of the rectangular cavity and the chiral selection of Troger's base-based macrocycles during their crystallization.
基金The authors are grateful for the financial support from the National Natural Science Foundation of China(Nos.21602055 and 51772091)Natural Science Foundation of Hunan Province(No.2017JJ3094)Research Foundation of Education Bureau of Hunan Province(No.18C1072).
文摘A novel good water-soluble macrocycle containing two pyridinium moieties was synthesized in high yield.It could form 1:1 complexes with neutral guests containing naphthalene or phenyl units in water.The water-soluble macrocycle can selectively encapsulate naphthalene to form a 1:1 complex over a variety of polycyclic aromatic hydrocarbons.
基金This work was supported by the National Natural Science Foundation of China(nos.21971235,91956119,22122111,and 92056109)Beijing National Laboratory for Molecular Sciences(no.BNLMS-CXXM-202105)Youth Innovation Promotion Association CAS(no.2019034).
文摘An efficient strategy for constructing chiral macrocycles with both thermally activated delayed fluorescence(TADF)and highly efficient circularly polarized electroluminescence(CPEL)properties was developed.Consequently,a pair of macrocyclic enantiomers(+)-(R,R)-MC and(−)-(S,S)-MC was synthesized by a combination of chiral octahydro-binaphthol moiety with triazine-based TADF skeleton.The chiral macrocycles exhibited obvious TADF properties with a lowΔE_(ST) of 0.067 eV,aggregation-induced emission behaviors,and high photoluminescence quantum yields of up to 79.7%.Moreover,the macrocyclic enantiomers showed mirror images in circular dichroism spectra and circularly polarized luminescence signals.Especially,the chiralmacrocycleswere suitable for the preparation of solution-processed circularly polarized organic light-emitting diodes,which displayed excellent device performances with a highmaximum external quantum efficiency of up to 17.1%,low-efficiency roll-off of 3.5%at 1000 cdm^(−2),andintenseCPELalong with electroluminescence dissymmetry factor of 1.7×10^(−3).
文摘以R-联萘酚、氯氰胺、间苯二胺、1,2二苯基乙二胺、乙二胺为原料合成了3个水溶性手性大环荧光传感器;利用核磁共振(1 H NMR和13 C NMR)、质谱、红外光谱验证了合成产物的结构,利用元素分析仪测定了其组成,并利用X射线衍射分析确定了单晶R-3的晶体结构.结果表明,R-3属于单斜晶系,P2(1)/n空间群,晶胞参数为:a=1.128 6nm,b=1.566 1nm,c=2.293 9nm,β=90°,Z=4,Dc=1.328g.cm-3,F(000)=1 684.
