The hierarchical assemblies of precise nanoparticles(NPs)have created materials with emergent properties and functionalities.However,the complex assemblies remain unclear at a precise scale.Here,we show the hierarchic...The hierarchical assemblies of precise nanoparticles(NPs)have created materials with emergent properties and functionalities.However,the complex assemblies remain unclear at a precise scale.Here,we show the hierarchical self-assembly of atomically precise gold nanoclusters(Au NCs)with molecular rotor-based ligands(MRL),featuring a double-layer surface.Compared to two other types of monolayer-protected(MLP)Au NCs,the significantly reduced surface density for MRL Au NCs profoundly influences their assembly behavior within the lattice.Furthermore,the long length of rotor-based ligands and the rotational freedom of the phenyl-rings of rotor-based ligands also facilitate the assembly of NCs.Our works elucidate the hierarchical assembly on a precise scale,suggesting that the rotor-based ligand’s strategy offers promising potential for designing well-defined and more complex structures in supercrystals.展开更多
Control over geometric curvature and chirality of assemblies in pure aqueous media is key to the design of responsive materials and molecular machines.Here we show how aggregate geometric curvature and chirality of mo...Control over geometric curvature and chirality of assemblies in pure aqueous media is key to the design of responsive materials and molecular machines.Here we show how aggregate geometric curvature and chirality of motor amphiphiles could be switched from bicontinuous calabashes to nanoribbons or from vesicles to nanoribbons by modulating rotor orientation direction with dual light/heat stimuli to influence spontaneous curvature in assemblies.The photoisomerization and thermal helix inversion processes of molecular motors have been studied at the molecular level,and the transformation of supramolecular assemblies has been investigated at the microscopic level.The morphological evolution of the calabash-shaped assembly can be kinetically captured,suggesting that the bicontinuous calabash-shaped structures are different from the bowl-shaped aggregates based on solvent-driven assembly upon the addition of non-solvent or solvent.The investigation of dual optical/thermal control of rotor orientation can provide a new strategy for tuning the geometric curvature and chirality of nanoassemblies at the nanoscale,arriving ultimately the clusteroluminescence through-space electronic communication at responsive supramolecular nanosystems.展开更多
A new bromethyl-substituted molecular rotor, [Cu（dabcoCH2Br）（H2O）Br3] （dabcoCH2Br＋=1-（2-bromethyl）-1,4-diazoniabi- cyclo[2.2.2]octane cation）, which belongs to a family of balomethyl-substituted molecular rot...A new bromethyl-substituted molecular rotor, [Cu（dabcoCH2Br）（H2O）Br3] （dabcoCH2Br＋=1-（2-bromethyl）-1,4-diazoniabi- cyclo[2.2.2]octane cation）, which belongs to a family of balomethyl-substituted molecular rotors, was synthesized and struc- turally characterized. The reversible phase transition at ca. 250 K was well established for this molecular rotor by thermal analyses, variable-temperature X-ray diffraction, and variable temperature dielectric measurements. The order-disorder trans- formation of the rotator part （dabco moiety） causes ferroelastic phase transition with an Aizu notation of mmmF2/m from high- temperature orthorhombic phase （Pbnm） to low-temperature monoclinic phase （P21/n）. More important, in reference to the density functional theory calculations and structural analyses, the key factors to tune the phase transition behaviors were dis- cussed in detail for this family of halomethyl-substituted molecular rotors.展开更多
As an extended model of conventional molecular rotors,a conceived construction of novel crystalline molecular rotor that simultaneously contains two discrete polar rotators is presented here.The supramolecular self-as...As an extended model of conventional molecular rotors,a conceived construction of novel crystalline molecular rotor that simultaneously contains two discrete polar rotators is presented here.The supramolecular self-assembly of 18-crown-6 host and two rotator-containing ion-pair guests affords a three-in-one cocrystal,(2-NH_(3)-iBuOH)(18-crown-6)[ZnBr_(3)(H_(2)O)],in which the hydroxyl group and aqua ligand both function as ultrasmall polar rotators.On the basis of the variable-temperature single-crystal X-ray diffraction,variable-temperature/frequency dielectric response,density functional theory calculations,and molecular dynamics simulations,it is found that such dual polar rotators experience a gradually enhanced rotation with increasing temperature,and more importantly,could be controlled by a reversible polar-to-polar structural phase transition,i.e.,from a“single-(polar rotator)”state at low-temperature phase to a“mixed-dual-(polar rotator)”state in the vicinity of transition,and to an unusual“synchronized-dual-(polar rotator)”state at high-temperature phase.展开更多
Molecular machines have attracted extensive attention due to their fancy concept and their potential to influence the science and technology.The dynamic motion of encapsulated metallic clusters is a distinctive charac...Molecular machines have attracted extensive attention due to their fancy concept and their potential to influence the science and technology.The dynamic motion of encapsulated metallic clusters is a distinctive character for endohedral metallofullerenes.For the development of molecular rotors based on metallofullerenes,the most challenging issue is how to control the motion of untouchable metallic cluster inside fullerene cage.In this work,we report a molecular brake hoop for the motion of metal atoms inside fullerene cage.A cycloparaphenylene of[12]CPP was employed to hoop the metallofullerene and produce two supramolecular complexes of Sc_(3)N@C_(80)⊂[12]CPP and Sc_(2)C_(2)@C_(82)⊂[12]CPP.Moreover,the temperature-dependent ^(45)Sc nuclear magnetic resonance spectroscopy(NMR)was employed to detect the motion of internal Sc_(3)N and Sc_(2)C_(2) clusters.^(45)Sc NMR results reveal that the[12]CPP can slow down the rotation of internal metallic cluster through host-guest interaction,and thus the[12]CPP can be considered as a molecular brake hoop for the internal metal motion of metallofullerenes.Furthermore,by means of this molecular brake hoop,the motion of metal atoms inside fullerene cage have expanded range of velocity.In addition,theoretical calculations on Sc_(3)N@C_(80)⊂[12]CPP were executed to illustrate the molecular orientation as well as internal Sc_(3)N rotation.This study would promote the research of endohedral metallofullerene as a molecular rotor.展开更多
粘度对细胞微环境的维持非常重要。检测细胞内的粘度一般采用分子转子,而目前大多数的分子转子发射波长较短,不利于生物成像,为此我们设计了基于扭转分子内电荷转移(TICT)机理,通过共轭双键连接吸电子基和给电子基的红光发射的分子转子2...粘度对细胞微环境的维持非常重要。检测细胞内的粘度一般采用分子转子,而目前大多数的分子转子发射波长较短,不利于生物成像,为此我们设计了基于扭转分子内电荷转移(TICT)机理,通过共轭双键连接吸电子基和给电子基的红光发射的分子转子2-(2-(4-氨基苯乙烯基)-4-H-吡喃-4-亚基)-丙二腈(DCM-NH_2)。DCM-NH_2的最大发射波长为631 nm,属于远红光,能有效减少生物背景,提高成像信噪比。该探针对粘度有很好的响应,具有非常宽的线性响应范围(0.6~458.6 c P),同时也具有较高的灵敏度。展开更多
The orientation switching of a single azobenzene molecule on Au(111)surface excited by tunneling electrons and/or photons has been demonstrated in recent experiments.Here we investigate the rotation behavior of this m...The orientation switching of a single azobenzene molecule on Au(111)surface excited by tunneling electrons and/or photons has been demonstrated in recent experiments.Here we investigate the rotation behavior of this molecular rotor by first-principles density functional theory(DFT)calculation.The anchor phenyl ring prefers adsorption on top of the fcc hollow site,simulated by a benzene molecule on close packed atomic surface.The adsorption energy for an azobenzene molecule on Au(111)surface is calculated to be about 1.76 eV.The rotational energy profile has been mapped with one of the phenyl rings pivots around the fcc hollow site,illustrating a potential barrier about 50 meV.The results are consistent with experimental observations and valuable for exploring a broad spectrum of molecules on this noble metal surface.展开更多
Three different methods are used to manipulate and control phthalocyanine based single molecular rotors on Au （111） surface： （1） changing the molecular structure to alter the rotation potential; （2） using the t...Three different methods are used to manipulate and control phthalocyanine based single molecular rotors on Au （111） surface： （1） changing the molecular structure to alter the rotation potential; （2） using the tunnelling current of the scanning tunnelling microscope （STM） to change the thermal equilibrium of the molecular rotor; （3） artificial manipulation of the molecular rotor to switch the rotation on or off by an STM tip. Furthermore, a molecular ＇gear wheel＇ is successfully achieved with two neighbouring molecules.展开更多
基金supported by the National Key R&D Program of China(No.2023YFC3404200)the National Natural Science Foundation of China(Nos.21974147,22325406)+1 种基金the 2022 Shanghai“Science and Technology Innovation Action Plan”Fundamental Research Project,China(No.22JC1401203)the Science Foundation of the Shanghai Municipal Science and Technology Commission,China(No.21dz2210100).
文摘The hierarchical assemblies of precise nanoparticles(NPs)have created materials with emergent properties and functionalities.However,the complex assemblies remain unclear at a precise scale.Here,we show the hierarchical self-assembly of atomically precise gold nanoclusters(Au NCs)with molecular rotor-based ligands(MRL),featuring a double-layer surface.Compared to two other types of monolayer-protected(MLP)Au NCs,the significantly reduced surface density for MRL Au NCs profoundly influences their assembly behavior within the lattice.Furthermore,the long length of rotor-based ligands and the rotational freedom of the phenyl-rings of rotor-based ligands also facilitate the assembly of NCs.Our works elucidate the hierarchical assembly on a precise scale,suggesting that the rotor-based ligand’s strategy offers promising potential for designing well-defined and more complex structures in supercrystals.
基金Science and Technology Program of Guangzhou,Grant/Award Number:201804010017National Natural Science Foundation of China,Grant/Award Number:21374137+1 种基金Natural Science Foundation of Guangdong Province,Grant/Award Number:2014A030313194Science and Technology Program of Guangdong Province,Grant/Award Number:2017A050506021。
文摘Control over geometric curvature and chirality of assemblies in pure aqueous media is key to the design of responsive materials and molecular machines.Here we show how aggregate geometric curvature and chirality of motor amphiphiles could be switched from bicontinuous calabashes to nanoribbons or from vesicles to nanoribbons by modulating rotor orientation direction with dual light/heat stimuli to influence spontaneous curvature in assemblies.The photoisomerization and thermal helix inversion processes of molecular motors have been studied at the molecular level,and the transformation of supramolecular assemblies has been investigated at the microscopic level.The morphological evolution of the calabash-shaped assembly can be kinetically captured,suggesting that the bicontinuous calabash-shaped structures are different from the bowl-shaped aggregates based on solvent-driven assembly upon the addition of non-solvent or solvent.The investigation of dual optical/thermal control of rotor orientation can provide a new strategy for tuning the geometric curvature and chirality of nanoassemblies at the nanoscale,arriving ultimately the clusteroluminescence through-space electronic communication at responsive supramolecular nanosystems.
基金supported by the National Natural Science Foundation of China(21290173,21301198)the National Basic Research Program of China(2012CB821706)the Natural Science Foundation of Guangdong(S2012030006240)
文摘A new bromethyl-substituted molecular rotor, [Cu（dabcoCH2Br）（H2O）Br3] （dabcoCH2Br＋=1-（2-bromethyl）-1,4-diazoniabi- cyclo[2.2.2]octane cation）, which belongs to a family of balomethyl-substituted molecular rotors, was synthesized and struc- turally characterized. The reversible phase transition at ca. 250 K was well established for this molecular rotor by thermal analyses, variable-temperature X-ray diffraction, and variable temperature dielectric measurements. The order-disorder trans- formation of the rotator part （dabco moiety） causes ferroelastic phase transition with an Aizu notation of mmmF2/m from high- temperature orthorhombic phase （Pbnm） to low-temperature monoclinic phase （P21/n）. More important, in reference to the density functional theory calculations and structural analyses, the key factors to tune the phase transition behaviors were dis- cussed in detail for this family of halomethyl-substituted molecular rotors.
基金supported by the National Natural Science Foundation of China(Nos.21971091,22071273,and 21821003)the Natural Science Foundation of Jiangxi Province(Nos.20192ACB20013,jxsq2018106041).
文摘As an extended model of conventional molecular rotors,a conceived construction of novel crystalline molecular rotor that simultaneously contains two discrete polar rotators is presented here.The supramolecular self-assembly of 18-crown-6 host and two rotator-containing ion-pair guests affords a three-in-one cocrystal,(2-NH_(3)-iBuOH)(18-crown-6)[ZnBr_(3)(H_(2)O)],in which the hydroxyl group and aqua ligand both function as ultrasmall polar rotators.On the basis of the variable-temperature single-crystal X-ray diffraction,variable-temperature/frequency dielectric response,density functional theory calculations,and molecular dynamics simulations,it is found that such dual polar rotators experience a gradually enhanced rotation with increasing temperature,and more importantly,could be controlled by a reversible polar-to-polar structural phase transition,i.e.,from a“single-(polar rotator)”state at low-temperature phase to a“mixed-dual-(polar rotator)”state in the vicinity of transition,and to an unusual“synchronized-dual-(polar rotator)”state at high-temperature phase.
基金supported by the National Natural Science Foundation of China(51972309,52022098)the Youth Innovation Promotion Association of Chinese Academy of Sciences(Y201910)Zhejiang Provincial Natural Science Foundation of China(LR22B010001)。
文摘Molecular machines have attracted extensive attention due to their fancy concept and their potential to influence the science and technology.The dynamic motion of encapsulated metallic clusters is a distinctive character for endohedral metallofullerenes.For the development of molecular rotors based on metallofullerenes,the most challenging issue is how to control the motion of untouchable metallic cluster inside fullerene cage.In this work,we report a molecular brake hoop for the motion of metal atoms inside fullerene cage.A cycloparaphenylene of[12]CPP was employed to hoop the metallofullerene and produce two supramolecular complexes of Sc_(3)N@C_(80)⊂[12]CPP and Sc_(2)C_(2)@C_(82)⊂[12]CPP.Moreover,the temperature-dependent ^(45)Sc nuclear magnetic resonance spectroscopy(NMR)was employed to detect the motion of internal Sc_(3)N and Sc_(2)C_(2) clusters.^(45)Sc NMR results reveal that the[12]CPP can slow down the rotation of internal metallic cluster through host-guest interaction,and thus the[12]CPP can be considered as a molecular brake hoop for the internal metal motion of metallofullerenes.Furthermore,by means of this molecular brake hoop,the motion of metal atoms inside fullerene cage have expanded range of velocity.In addition,theoretical calculations on Sc_(3)N@C_(80)⊂[12]CPP were executed to illustrate the molecular orientation as well as internal Sc_(3)N rotation.This study would promote the research of endohedral metallofullerene as a molecular rotor.
文摘粘度对细胞微环境的维持非常重要。检测细胞内的粘度一般采用分子转子,而目前大多数的分子转子发射波长较短,不利于生物成像,为此我们设计了基于扭转分子内电荷转移(TICT)机理,通过共轭双键连接吸电子基和给电子基的红光发射的分子转子2-(2-(4-氨基苯乙烯基)-4-H-吡喃-4-亚基)-丙二腈(DCM-NH_2)。DCM-NH_2的最大发射波长为631 nm,属于远红光,能有效减少生物背景,提高成像信噪比。该探针对粘度有很好的响应,具有非常宽的线性响应范围(0.6~458.6 c P),同时也具有较高的灵敏度。
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21961142021,11774395,91753136,and 11727902)the Beijing Natural Science Foundation,China(Grant No.4181003)the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant Nos.XDB30201000 and XDB28000000).
文摘The orientation switching of a single azobenzene molecule on Au(111)surface excited by tunneling electrons and/or photons has been demonstrated in recent experiments.Here we investigate the rotation behavior of this molecular rotor by first-principles density functional theory(DFT)calculation.The anchor phenyl ring prefers adsorption on top of the fcc hollow site,simulated by a benzene molecule on close packed atomic surface.The adsorption energy for an azobenzene molecule on Au(111)surface is calculated to be about 1.76 eV.The rotational energy profile has been mapped with one of the phenyl rings pivots around the fcc hollow site,illustrating a potential barrier about 50 meV.The results are consistent with experimental observations and valuable for exploring a broad spectrum of molecules on this noble metal surface.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 60771037 and 10774176)the National Basic Research Program of China (Grant No. 2007CB936802)
文摘Three different methods are used to manipulate and control phthalocyanine based single molecular rotors on Au （111） surface： （1） changing the molecular structure to alter the rotation potential; （2） using the tunnelling current of the scanning tunnelling microscope （STM） to change the thermal equilibrium of the molecular rotor; （3） artificial manipulation of the molecular rotor to switch the rotation on or off by an STM tip. Furthermore, a molecular ＇gear wheel＇ is successfully achieved with two neighbouring molecules.
