Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designi...Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge.Here we report two discrete trefoil-shaped metallacycle S1 and metallacage s2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands.The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic'Mitsubishi motif.The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2.The formed metallacage S2 possesses a molecular weight up to 36 kDa,diameter 6.6 nm and height 3.0 nm.All supramolecular coordination complexes were fully characterized by NMR spectroscopy(^(1)H NMR,2D COSY,2D NOESY,2D DOSY),high-resolution electrospray ionization mass sectrometry ESI-MS.ESI-TWIM-MS,TEM and AFM.展开更多
Two families of cyclopentadienyl(Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes,namely[Ln{η^(5):σ-Me_(2)C(C_(5)H_(4))(C_(2)B_(10)H_(10))}_(2)][Li(DME)_(3)](1Ln,Ln=Tb,Dy,Ho,Er)and[2-THF-2'-(μ^...Two families of cyclopentadienyl(Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes,namely[Ln{η^(5):σ-Me_(2)C(C_(5)H_(4))(C_(2)B_(10)H_(10))}_(2)][Li(DME)_(3)](1Ln,Ln=Tb,Dy,Ho,Er)and[2-THF-2'-(μ^(2)-Cl)Li(THF)_"(3)-2,2'-Ln(nido-1,7-C_(2)B_(9)H_(11))Cp*](2Dy),were synthesized.Family of 1Ln has been proposed based on the mixing-ligands idea by linking Cp and nido-dicarborllide.However,the carborane cage of[Me_(2)C(C_(5)H_(4))(C_(2)B_(10)H_(10))]_(2)−deprotons and forms a mono-C−anion rather than deboron to form dicarborllide dianion.Hence,the family of 1Ln features a dysprosocenium skeleton with extra two coordination of C−anions of carborllides.Such coordination geometry is more like a tetrahedron if abstracting the centroids of two coordinated Cp rings.In this cubic-type geometry,no significant magnetic axiality is presented;only 1Dy and 1Tb show field-induced slow magnetic relaxation behavior below 10 K.Inspired by 1Ln,the free pentamethylcyclopentadienyl(Cp^(*−))and nido-dicarborllide ligands are used to sandwich central Dy3+ion,achieving heteroleptic complex 2Dy.The bending angle by linking the centroid of Cp^(*−),Dy^(3+)and C_(2)B_(3)^(2−)in 2Dy is increased to 132.8(1)°.As such,the effective energy barrier for magnetic reversal(Ueff)and magnetic blocking temperature TB(ZFC)are both increased(Ueff=616(10)K;TB=6 K).The effort of further enhancing Ueff and TB in such heteroleptic organolanthanide sandwiches should rely on keeping increasing the ligand axiality.展开更多
The size complementarity between a host and a vip is a critical prerequisite for selective molecular recognition.Numerous artificial host systems have been designed to achieve size-selective recognition and chemical...The size complementarity between a host and a vip is a critical prerequisite for selective molecular recognition.Numerous artificial host systems have been designed to achieve size-selective recognition and chemical transformations.However,the inherent challenge lies in the fixed selectivity governed by a size-exclusion mechanism dictated by the host's structure.Modulating the selectivity necessitates structural modifications of hosts.Examples of host systems with modifiable sizeselectivity are rare.In this study,we present an approach to modulating vip-selectivity via endo-functionalization of supramolecular cavities.Heteroleptic Pd_(2)A_(3)B-cages are constructed with a Pd_(2)A_(3)precursor or directly from palladium ions and relevant ligands.Furthermore,the simultaneous and selective formation of multiple hetero-cages was achieved by simply mixing PdIIand the free ligands in a one-pot reaction.The fidelity of the assembly process relies on cooperative steric control at the periphery and within the cavity of the hetero-cages,respectively.The central steric group also functions as the endohedral moiety.Variations of the endohedral groups facilitate facile and modular derivatization of the microenvironment within the cages,enabling the fine-tuning of vip binding affinities as evidenced by titration experiments.This strategy offers a new solution for the development of customized host structures.展开更多
A variety of heteroleptic ruthenium sensitizers have been engineered and synthesized because of their higher light-harvesting efficiency and lower charge-recombination possibility than the well known homoleptic N3 dye...A variety of heteroleptic ruthenium sensitizers have been engineered and synthesized because of their higher light-harvesting efficiency and lower charge-recombination possibility than the well known homoleptic N3 dye. As such, a great deal of atten- tion has been focused on sensitizers with the general formula Ru（ancillary-ligand）（anchoring-ligand）（NCS）2, among which important examples are Ru（4,4＇-bis（5-hexylthiophen-2-yl）-2,2＇-bipyridine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （C101） and Ru（N-（4-butoxyphenyl）-N-2-pyridinyl-2-pyridinamine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （J13）. In order to simulate experimental conditions with different pH values, the photosensitizing processes of these sensitizers pos- sessing different degrees of deprotonation （2I-I, lit to OH） have been explored theoretically in this work. Their ground/excited state geometries, electronic structures and spectroscopic properties are first calculated using density functional theory （DFT） and time-dependent DFT （TDDFT）. The absorption and emission spectra of all the complexes in acetonitrile solution are also predicted at the TDDFT （B3LYP） level. The calculated results show that the ancillary ligand contributes to the molecular or- bital （MO） energy levels and absorption transitions. It is intriguing to observe that the introduction of a thiophene group into the ancillary ligand leads directly to the increased energy of the absorption transitions in the 380-450 nm region. The calcula- tions reveal that although deprotonation destabilizes the overall frontier MOs of the chromophores, it tends to exert a greater influence on the unoccupied orbitals than on the occupied orbitals. Consequently, an obvious blue shift was observed for the absorptions and emissions in going from 21-1, 1H to OH. Finally, the optimal degree of deprotonation for C101 and J13 has al- so been evaluated, which is expected to lead to further improvements in the performance of dye-sensitized solar cells （DSSCs） coated with such sensitizers.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22101060 for M.C.,and 21971257 for P.w.)the Guangdong Natural Science Foundation(No.2022A1515012187 to M.C.)the Science and Technology Research Project of Guangzhou(Nos.202201020201 for M.C.and 202102010432 for ZJ..Science and technology support plan of Guizhou Province[2019]2860 for W.L.The authors gratefully acknowledge the Center for Advanced Research in CSU for the NMR measurements.
文摘Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge.Here we report two discrete trefoil-shaped metallacycle S1 and metallacage s2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands.The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic'Mitsubishi motif.The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2.The formed metallacage S2 possesses a molecular weight up to 36 kDa,diameter 6.6 nm and height 3.0 nm.All supramolecular coordination complexes were fully characterized by NMR spectroscopy(^(1)H NMR,2D COSY,2D NOESY,2D DOSY),high-resolution electrospray ionization mass sectrometry ESI-MS.ESI-TWIM-MS,TEM and AFM.
基金the assistance of the project supported by the National Natural Science Foundation of China(22375157,22401227)the Programme of Introducing Talents of Discipline to Universities(B23025)+3 种基金State Key Laboratory of Electrical Insulation and Power Equipment(EIPE23402,EIPE23405)the China Postdoctoral Science Foundation(2023M742783,GZB20240599)"Medical-Engineering Cross Project of the First Affiliated Hospital of XJTU(QYJCo2)"Shaanxi Postdoctoral Science Foundation(2023BSHYDZZ12)and the"Scientists+Engineers"Team Building Project of Qin Chuang Yuan(2022KXJ-088).
文摘Two families of cyclopentadienyl(Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes,namely[Ln{η^(5):σ-Me_(2)C(C_(5)H_(4))(C_(2)B_(10)H_(10))}_(2)][Li(DME)_(3)](1Ln,Ln=Tb,Dy,Ho,Er)and[2-THF-2'-(μ^(2)-Cl)Li(THF)_"(3)-2,2'-Ln(nido-1,7-C_(2)B_(9)H_(11))Cp*](2Dy),were synthesized.Family of 1Ln has been proposed based on the mixing-ligands idea by linking Cp and nido-dicarborllide.However,the carborane cage of[Me_(2)C(C_(5)H_(4))(C_(2)B_(10)H_(10))]_(2)−deprotons and forms a mono-C−anion rather than deboron to form dicarborllide dianion.Hence,the family of 1Ln features a dysprosocenium skeleton with extra two coordination of C−anions of carborllides.Such coordination geometry is more like a tetrahedron if abstracting the centroids of two coordinated Cp rings.In this cubic-type geometry,no significant magnetic axiality is presented;only 1Dy and 1Tb show field-induced slow magnetic relaxation behavior below 10 K.Inspired by 1Ln,the free pentamethylcyclopentadienyl(Cp^(*−))and nido-dicarborllide ligands are used to sandwich central Dy3+ion,achieving heteroleptic complex 2Dy.The bending angle by linking the centroid of Cp^(*−),Dy^(3+)and C_(2)B_(3)^(2−)in 2Dy is increased to 132.8(1)°.As such,the effective energy barrier for magnetic reversal(Ueff)and magnetic blocking temperature TB(ZFC)are both increased(Ueff=616(10)K;TB=6 K).The effort of further enhancing Ueff and TB in such heteroleptic organolanthanide sandwiches should rely on keeping increasing the ligand axiality.
基金supported by the National Natural Science Foundation of China(22171192)the“1000-Youth Talents Program”,the Science&Technology Department of Sichuan Province(2022ZYD0050)the Fundamental Research Funds for the Central Universities。
文摘The size complementarity between a host and a vip is a critical prerequisite for selective molecular recognition.Numerous artificial host systems have been designed to achieve size-selective recognition and chemical transformations.However,the inherent challenge lies in the fixed selectivity governed by a size-exclusion mechanism dictated by the host's structure.Modulating the selectivity necessitates structural modifications of hosts.Examples of host systems with modifiable sizeselectivity are rare.In this study,we present an approach to modulating vip-selectivity via endo-functionalization of supramolecular cavities.Heteroleptic Pd_(2)A_(3)B-cages are constructed with a Pd_(2)A_(3)precursor or directly from palladium ions and relevant ligands.Furthermore,the simultaneous and selective formation of multiple hetero-cages was achieved by simply mixing PdIIand the free ligands in a one-pot reaction.The fidelity of the assembly process relies on cooperative steric control at the periphery and within the cavity of the hetero-cages,respectively.The central steric group also functions as the endohedral moiety.Variations of the endohedral groups facilitate facile and modular derivatization of the microenvironment within the cages,enabling the fine-tuning of vip binding affinities as evidenced by titration experiments.This strategy offers a new solution for the development of customized host structures.
基金supported by the National Natural Science Foundation of China (20703015,20973076,and 21003057)Program for New Century Excellent Talents in Heilongjiang Provincial University of China (1154-NCET-010)
文摘A variety of heteroleptic ruthenium sensitizers have been engineered and synthesized because of their higher light-harvesting efficiency and lower charge-recombination possibility than the well known homoleptic N3 dye. As such, a great deal of atten- tion has been focused on sensitizers with the general formula Ru（ancillary-ligand）（anchoring-ligand）（NCS）2, among which important examples are Ru（4,4＇-bis（5-hexylthiophen-2-yl）-2,2＇-bipyridine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （C101） and Ru（N-（4-butoxyphenyl）-N-2-pyridinyl-2-pyridinamine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （J13）. In order to simulate experimental conditions with different pH values, the photosensitizing processes of these sensitizers pos- sessing different degrees of deprotonation （2I-I, lit to OH） have been explored theoretically in this work. Their ground/excited state geometries, electronic structures and spectroscopic properties are first calculated using density functional theory （DFT） and time-dependent DFT （TDDFT）. The absorption and emission spectra of all the complexes in acetonitrile solution are also predicted at the TDDFT （B3LYP） level. The calculated results show that the ancillary ligand contributes to the molecular or- bital （MO） energy levels and absorption transitions. It is intriguing to observe that the introduction of a thiophene group into the ancillary ligand leads directly to the increased energy of the absorption transitions in the 380-450 nm region. The calcula- tions reveal that although deprotonation destabilizes the overall frontier MOs of the chromophores, it tends to exert a greater influence on the unoccupied orbitals than on the occupied orbitals. Consequently, an obvious blue shift was observed for the absorptions and emissions in going from 21-1, 1H to OH. Finally, the optimal degree of deprotonation for C101 and J13 has al- so been evaluated, which is expected to lead to further improvements in the performance of dye-sensitized solar cells （DSSCs） coated with such sensitizers.
