A ditopic ligand bpy-cyclam(L)and its heterometallo-binuclear complex Ru(bpy)_2(bpy-cyclam-Ni)(ClO_4)_43H_2O(3)designed for use in the catalytic photoreduction of carbon dioxide have been newly synthesized and charact...A ditopic ligand bpy-cyclam(L)and its heterometallo-binuclear complex Ru(bpy)_2(bpy-cyclam-Ni)(ClO_4)_43H_2O(3)designed for use in the catalytic photoreduction of carbon dioxide have been newly synthesized and characterized.The protonation constants of L were also determined.展开更多
A series of polymetallic Cu_((I))assemblies C_(1-4)was selectively obtained by self-assembly of a preorganized trimetallic precursor B with 3,3’-bipyridine ligand L_(1)and structurally related longer ligands C_(2-4),...A series of polymetallic Cu_((I))assemblies C_(1-4)was selectively obtained by self-assembly of a preorganized trimetallic precursor B with 3,3’-bipyridine ligand L_(1)and structurally related longer ligands C_(2-4),respectively,allowing to investigate the impact of ligands’backbones on architectures on the derivatives C_(1-4).While linkers L_(1)and L_(2)led to the formation of 1D coordination polymers(C_(1,2)),the newly prepared alloxazine-functionalized ligands L_(3)and L_(4),promoting the appearance of steric constraints andπ-πinteractions,led to the formation of discrete hexametallacycles(C_(3,4)).Structural characterization via X-ray diffraction confirmed the role of ligand design in determining the final architectures.The solid-state photophysical properties of ligands L_(3)and L_(4),trimetallic precursor B and derivatives C_(1-4).are reported.L_(3)and L_(4)exhibit weak yellow fluorescence at room temperature(RT),while the trimetallic precursor B displays intense yellow ^(3)MLCT phosphorescence at RT.Assemblies C_(1-4)show varied photophysical behaviors including ^(3)MLCT phosphorescence for C_(1),ligand centered phosphorescence and fluorescence for C2and C4,respectively,while C3is non-emissive.This study provides new insights into the steric and electronic factors governing Cu_((I))-based luminescent materials’preparation,highlighting diverse photophysical behaviors including efficient RT emission performances.展开更多
The design,synthesis and characterization of two new triptycene-containing ditopic Pt(Ⅱ)organometallic complexes is being reported.These complexes comprise of two peripheral bis(trans-trialkylphosphine)-platinum unit...The design,synthesis and characterization of two new triptycene-containing ditopic Pt(Ⅱ)organometallic complexes is being reported.These complexes comprise of two peripheral bis(trans-trialkylphosphine)-platinum units either directly σ-bonded to the central triptycene moiety or connected via a bridging ethynyl spacer linkage.The potential utility of these organometallic complexes as ditopic acceptor building blocks for the construction of neutral metallasupramolecular macrocycles containing the triptycene motif is explored.Triptycene motif containing supramolecules were characterized using multinuclear NMR(including ^(1)H DOSY),mass spectrometry(MALDI-TOF-MS)and elemental analyses.While the selfassembly of a longer acceptor linker with a terephthalate group results in the formation of a[3+3]selfassembled macrocycle,the use of a relatively shorter acceptor linker yields the corresponding[2+2]supramolecular framework.The shapes and dimensions of these supramolecular structures were also predicted by geometry optimization using PM6 semiempirical molecular orbital methods and the results corroborate well with the experimental observations.These two self-assembled macrocycles are unique examples of triptycene-based neutral“platinamacrocycles”reported in the literature to date.An investigation as to how the shape and size of the resulting discrete supramolecular framework is affected upon changing the length and rigidity of the triptycene-based acceptor linkers is discussed.展开更多
In this study,we report the synthesis of five one-dimensional Zn(II)-based metallo-supramolecular polymers P0–4 through 1:1 complexation of Zn(SO_(3)CF_(3))_(2)or Zn(ClO_(4))_(2)with ditopic ligands L^(0–4)which con...In this study,we report the synthesis of five one-dimensional Zn(II)-based metallo-supramolecular polymers P0–4 through 1:1 complexation of Zn(SO_(3)CF_(3))_(2)or Zn(ClO_(4))_(2)with ditopic ligands L^(0–4)which contain two pyridine-dioxazole(pybox)units connected by a rigid conjugated oligo(1,4-phenylene)linker.The new Zn(II)-based polymers displayed relatively high quantum yields in solution and the solid state and showed tunable luminescent colors from blue to yellow owing to the conjugation effect of the ligand and the intra-ligand charge transfer(ILCT)between the coordination site and the chromophore of the ligand.Moreover,the polymer solution could exhibit white light emission by simply regulating the metal/ligand ratio or mixing different polymers.The polymers have been further explored as fluorescent chemosensors(FCs)for detecting nitroaromatic explosives.Among others,P1 possessed the highest capability for detecting picric acid(PA).展开更多
The synthesis of heterotrimetallic molecular cages is reported.The assemblies contain three types of coordination compounds:Fe^(Ⅱ)clathrochelate complexes,Au_(3)^(Ⅰ)(pyrazolate)3 complexes,and[Pd^(Ⅱ)(pyridine)_(4)]...The synthesis of heterotrimetallic molecular cages is reported.The assemblies contain three types of coordination compounds:Fe^(Ⅱ)clathrochelate complexes,Au_(3)^(Ⅰ)(pyrazolate)3 complexes,and[Pd^(Ⅱ)(pyridine)_(4)]^(2+)complexes.The cages were obtained in a stepwise fashion.A nanometer-sized metalloligand with three terminal 3-pyridyl donor groups was prepared by connection of three Fe^(Ⅱ)clathrochelate complexes via a central Au_(3)(pyrazolate)3 complex.A related strategy was employed for the synthesis of a ditopic N-donor ligand with two functionalized Fe^(Ⅱ)clathrochelate complexes.Combining the tritopic ligand with[Pd(CH_(3)CN)_(4)](BF_(4))_(2)resulted in the clean formation of a spherical Pd_(6)^(Ⅱ)Fe_(24)^(Ⅱ)Au_(24)^(Ⅰ)coordination cage with a diameter of∼4.1 nm and a molecular weight of 21 kDa.The ditopic metalloligand was used for the construction of a Pd_(2)^(Ⅱ)Pd_(8)^(Ⅱ)Au_(12)^(Ⅰ)cage.展开更多
In this study,a pair of cyanide-bridged{Fe_(2)Co}-based coordination polymers,{[(^(Pz)Tp)Fe(CN)_(3)]_(2)Co(L)_(2)}·_(4)H_(2)O(1)and{[(Tp)Fe(CN)_(3)]_(2)Co(L)_(2)}·_(3)H_(2)O·CH_(3)OH(2),was synthesized ...In this study,a pair of cyanide-bridged{Fe_(2)Co}-based coordination polymers,{[(^(Pz)Tp)Fe(CN)_(3)]_(2)Co(L)_(2)}·_(4)H_(2)O(1)and{[(Tp)Fe(CN)_(3)]_(2)Co(L)_(2)}·_(3)H_(2)O·CH_(3)OH(2),was synthesized by assembling Co^(Ⅱ) with[(^(Pz)Tp)Fe^(Ⅲ)(CN)_(3)]^(-)(^(Pz)Tp:tetrakis(pyrazolyl)borate)and the less hindered[(Tp)Fe^(Ⅲ)(CN)_(3)]-(Tp:tris(pyrazolyl)borate)in the presence of the asymmetric ditopic ligand L(4-(1H-imidazol-5-ylmethylene-amino)-4H-1,2,4-triazole).展开更多
Deoxyribonucleic acid(DNA)is a biologically essential molecule that holds a genetic code.DNA also carries oxyanionic phosphate units regularly and densely along its double-stranded,helical structure.Although several s...Deoxyribonucleic acid(DNA)is a biologically essential molecule that holds a genetic code.DNA also carries oxyanionic phosphate units regularly and densely along its double-stranded,helical structure.Although several strategies have been reported to materialize DNA,the mechanical properties are not comparable to those of oil-based commodity plastics.Here,we report a DNA-based supramolecular plastic(^(DNA)SP),which is mechanically stiff yet readily dissociable into metabolizable monomers by the action of salt.We mixed oligo-DNA and a ditopic guanidinium salt(Gu_(2))serving as the anionic and cationic monomers,respectively,in deionized water,forming a cross-linked polymer network via a multivalent saltbridge interaction.This polymer network spontaneously phase-separated into a condensed phase,while the counterions of the two monomers remained in the original water-rich phase;thus,physically separated fromthe polymer network.Isolation of the condensed phase,followed by drying,formed ^(DNA)SP,a glassy,densely packed,thermally stable(T_(5%)=216°C),and optically transparent plastic,with a refractive index(n)of 1.46 and mechanical stiffness(E_(IT))of 8.2 GPa comparable to thermoset commodity polymers.One issue to address is that ^(DNA)SP is brittle,certainly due to the dense negative charges in the DNA component.展开更多
Metal-based secondary building unit and the shape of organic ligands are the two crucial factors for determining the final topology of metal-organic materials.A careful choice of organic and inorganic structural build...Metal-based secondary building unit and the shape of organic ligands are the two crucial factors for determining the final topology of metal-organic materials.A careful choice of organic and inorganic structural building units occasionally produces unexpected structures,facilitating deeper fundamental understanding of coordination-driven self-assembly behind metal-organic materials.Here,we have synthesized a triangular metal-organic polygon(MOT-1),assembled from bulky tetramethyl terephthalate and Zr-based secondary building unit.Surprisingly,the Zr-based secondary building unit serves as an unusual ditopic Zr-connector,toform metal-organic polygon MOT-1,proven to be a good candidate for water adsorption with recyclability.This study highlights the interplay of the geometrically frustrated ligand and secondary building unit in controlling the connectivity of metal-organic polygon.Such a strategy can be further used to unveil a new class of metal-organic materials.展开更多
Diffusion reaction of the labile building block Mg（acacCN）2 （acacCN= 3-cyanoacetylacetonate） with silver salts leads to a series of solvated Mg/Ag bimetallic coordination polymers with composition [Mg（acacCN）aAg...Diffusion reaction of the labile building block Mg（acacCN）2 （acacCN= 3-cyanoacetylacetonate） with silver salts leads to a series of solvated Mg/Ag bimetallic coordination polymers with composition [Mg（acacCN）aAg].solvent. Despite their common stoichiometry, the topology of these polymers depends on the solvent of crystallization. The two-dimensional coordination compound [Mg（acacCN）aAg]-4CHCl3 in space group P]- is obtained as platelet-shaped crystals from a mixture of methanol and chloroform. When kept in the reaction mixture, these thin plates within one week convert to isometric tetrahedral crystals of the 3D network [Mg（acacCN）3Ag]. 2CHC13 in the cubic space group/9213. The transformation reaction proceeds via dissolution and recrystallization. The co-crystallized solvent molecules play an important role for stabilizing the target structure： They subtend Cl...Cl contacts and interact via non- classical C-H.-. O hydrogen bonds with the coordination framework. In the new cubic coordination network, both Mg（II） and Ag（I） adopt octahedral coordination, with unprecedented face-sharing by bridging O atoms of three acetylacetonato moieties. Prolonged standing of [Mg（acacCN）3Ag]-2CHCl3 in the reaction medium leads to further degradation, under formation of [Ag（acacCN）].展开更多
文摘A ditopic ligand bpy-cyclam(L)and its heterometallo-binuclear complex Ru(bpy)_2(bpy-cyclam-Ni)(ClO_4)_43H_2O(3)designed for use in the catalytic photoreduction of carbon dioxide have been newly synthesized and characterized.The protonation constants of L were also determined.
基金supported by the CNRS,the ANR(ANR PRC SMAC and ANR PRCI SUPRALUM),the French‘Ministère de l’Enseignement Supérieur,de la Recherche et de l’Innovation’and the French‘Ministère des Affaires Etrangères’the Alexander von Humboldt Foundation for a fellowship for experienced researchersupport from the University of Strasbourg Agence Nationale de la Recherche(ANR)through BattAllox project ANR-20-CE05-0005 are acknowledged.
文摘A series of polymetallic Cu_((I))assemblies C_(1-4)was selectively obtained by self-assembly of a preorganized trimetallic precursor B with 3,3’-bipyridine ligand L_(1)and structurally related longer ligands C_(2-4),respectively,allowing to investigate the impact of ligands’backbones on architectures on the derivatives C_(1-4).While linkers L_(1)and L_(2)led to the formation of 1D coordination polymers(C_(1,2)),the newly prepared alloxazine-functionalized ligands L_(3)and L_(4),promoting the appearance of steric constraints andπ-πinteractions,led to the formation of discrete hexametallacycles(C_(3,4)).Structural characterization via X-ray diffraction confirmed the role of ligand design in determining the final architectures.The solid-state photophysical properties of ligands L_(3)and L_(4),trimetallic precursor B and derivatives C_(1-4).are reported.L_(3)and L_(4)exhibit weak yellow fluorescence at room temperature(RT),while the trimetallic precursor B displays intense yellow ^(3)MLCT phosphorescence at RT.Assemblies C_(1-4)show varied photophysical behaviors including ^(3)MLCT phosphorescence for C_(1),ligand centered phosphorescence and fluorescence for C2and C4,respectively,while C3is non-emissive.This study provides new insights into the steric and electronic factors governing Cu_((I))-based luminescent materials’preparation,highlighting diverse photophysical behaviors including efficient RT emission performances.
基金the Department of Science and Technology,Govt.of India,New Delhi(DST no:SR/FT/CS-028/2009)the Indian Institute of Technology Patna for financial support.
文摘The design,synthesis and characterization of two new triptycene-containing ditopic Pt(Ⅱ)organometallic complexes is being reported.These complexes comprise of two peripheral bis(trans-trialkylphosphine)-platinum units either directly σ-bonded to the central triptycene moiety or connected via a bridging ethynyl spacer linkage.The potential utility of these organometallic complexes as ditopic acceptor building blocks for the construction of neutral metallasupramolecular macrocycles containing the triptycene motif is explored.Triptycene motif containing supramolecules were characterized using multinuclear NMR(including ^(1)H DOSY),mass spectrometry(MALDI-TOF-MS)and elemental analyses.While the selfassembly of a longer acceptor linker with a terephthalate group results in the formation of a[3+3]selfassembled macrocycle,the use of a relatively shorter acceptor linker yields the corresponding[2+2]supramolecular framework.The shapes and dimensions of these supramolecular structures were also predicted by geometry optimization using PM6 semiempirical molecular orbital methods and the results corroborate well with the experimental observations.These two self-assembled macrocycles are unique examples of triptycene-based neutral“platinamacrocycles”reported in the literature to date.An investigation as to how the shape and size of the resulting discrete supramolecular framework is affected upon changing the length and rigidity of the triptycene-based acceptor linkers is discussed.
基金supported by the National Natural Science Foundation of China(no.21371043 and 21302035)the Fundamental Research Funds for the Central Universities(2014HGCH0009)for financial support.We thank Mr Chao Zhang and Prof.Hong-Bo Lu(HFUT)for help in the measurement of absolute photoluminescence quantum yield and Prof.Xun Hong(USTC)for help in the SEM measurement.We also thank Prof.Zhan-Ting Li(Fudan University)for the sustained support and helpful discussions.
文摘In this study,we report the synthesis of five one-dimensional Zn(II)-based metallo-supramolecular polymers P0–4 through 1:1 complexation of Zn(SO_(3)CF_(3))_(2)or Zn(ClO_(4))_(2)with ditopic ligands L^(0–4)which contain two pyridine-dioxazole(pybox)units connected by a rigid conjugated oligo(1,4-phenylene)linker.The new Zn(II)-based polymers displayed relatively high quantum yields in solution and the solid state and showed tunable luminescent colors from blue to yellow owing to the conjugation effect of the ligand and the intra-ligand charge transfer(ILCT)between the coordination site and the chromophore of the ligand.Moreover,the polymer solution could exhibit white light emission by simply regulating the metal/ligand ratio or mixing different polymers.The polymers have been further explored as fluorescent chemosensors(FCs)for detecting nitroaromatic explosives.Among others,P1 possessed the highest capability for detecting picric acid(PA).
基金supported by theÉcole Polytechnique Fédérale de Lausanne(EPFL).
文摘The synthesis of heterotrimetallic molecular cages is reported.The assemblies contain three types of coordination compounds:Fe^(Ⅱ)clathrochelate complexes,Au_(3)^(Ⅰ)(pyrazolate)3 complexes,and[Pd^(Ⅱ)(pyridine)_(4)]^(2+)complexes.The cages were obtained in a stepwise fashion.A nanometer-sized metalloligand with three terminal 3-pyridyl donor groups was prepared by connection of three Fe^(Ⅱ)clathrochelate complexes via a central Au_(3)(pyrazolate)3 complex.A related strategy was employed for the synthesis of a ditopic N-donor ligand with two functionalized Fe^(Ⅱ)clathrochelate complexes.Combining the tritopic ligand with[Pd(CH_(3)CN)_(4)](BF_(4))_(2)resulted in the clean formation of a spherical Pd_(6)^(Ⅱ)Fe_(24)^(Ⅱ)Au_(24)^(Ⅰ)coordination cage with a diameter of∼4.1 nm and a molecular weight of 21 kDa.The ditopic metalloligand was used for the construction of a Pd_(2)^(Ⅱ)Pd_(8)^(Ⅱ)Au_(12)^(Ⅰ)cage.
基金supported by the National Natural Science Foundation of China(grants 22222103,22173015,22025101,21901133 and 21871039)the Fundamental Research Funds for the Central Universities,China。
文摘In this study,a pair of cyanide-bridged{Fe_(2)Co}-based coordination polymers,{[(^(Pz)Tp)Fe(CN)_(3)]_(2)Co(L)_(2)}·_(4)H_(2)O(1)and{[(Tp)Fe(CN)_(3)]_(2)Co(L)_(2)}·_(3)H_(2)O·CH_(3)OH(2),was synthesized by assembling Co^(Ⅱ) with[(^(Pz)Tp)Fe^(Ⅲ)(CN)_(3)]^(-)(^(Pz)Tp:tetrakis(pyrazolyl)borate)and the less hindered[(Tp)Fe^(Ⅲ)(CN)_(3)]-(Tp:tris(pyrazolyl)borate)in the presence of the asymmetric ditopic ligand L(4-(1H-imidazol-5-ylmethylene-amino)-4H-1,2,4-triazole).
基金financially supported by the Japan Society for the Promotion of Science(JSPS)Grant-in-Aid for Specially Promoted Research(grant no.23H05408)on“Solid-State Materials Science of Supramolecular Polymers and Their Applications”This work was also financially supported by the Rikagaku Kenkyūsho Transformative Research Innovation Platform of(RIKEN TRIP)Initiative Polymer Chemistry,Japan.Y.H.acknowledges the financial support from the Junior Research Associate(JRA)program at RIKEN for graduate students.
文摘Deoxyribonucleic acid(DNA)is a biologically essential molecule that holds a genetic code.DNA also carries oxyanionic phosphate units regularly and densely along its double-stranded,helical structure.Although several strategies have been reported to materialize DNA,the mechanical properties are not comparable to those of oil-based commodity plastics.Here,we report a DNA-based supramolecular plastic(^(DNA)SP),which is mechanically stiff yet readily dissociable into metabolizable monomers by the action of salt.We mixed oligo-DNA and a ditopic guanidinium salt(Gu_(2))serving as the anionic and cationic monomers,respectively,in deionized water,forming a cross-linked polymer network via a multivalent saltbridge interaction.This polymer network spontaneously phase-separated into a condensed phase,while the counterions of the two monomers remained in the original water-rich phase;thus,physically separated fromthe polymer network.Isolation of the condensed phase,followed by drying,formed ^(DNA)SP,a glassy,densely packed,thermally stable(T_(5%)=216°C),and optically transparent plastic,with a refractive index(n)of 1.46 and mechanical stiffness(E_(IT))of 8.2 GPa comparable to thermoset commodity polymers.One issue to address is that ^(DNA)SP is brittle,certainly due to the dense negative charges in the DNA component.
基金Korea Environment Industry&Technology Institute(KEITI)through Public Technology Program based on Environmental Policy Program,funded by Korea M inistry of Environment(MOE)(No.2018000210002)National Research Foundation(NRF)of Korea(Nos.NRF-2016R1A5A1009405,NRF-2017M3C1B4051161)D.-W.L.and H.K.acknowledge the support from the ACCEL program Japan Science and Technology Agency(JST),JPMJAC1501.J.K.acknowledges the support from NRF Grant funded by the Korean Government(No.NRF-2018H1A2A1061391-Global Ph.D.Fellowship Program).We acknowledge the Pohang Accelerator Laboratory(PAL)for 2D beamline use(2019-1st-2D-038).We would like to thank Hyeonsoo Chofor providing 3D models for possible structures shown in Fig.8.
文摘Metal-based secondary building unit and the shape of organic ligands are the two crucial factors for determining the final topology of metal-organic materials.A careful choice of organic and inorganic structural building units occasionally produces unexpected structures,facilitating deeper fundamental understanding of coordination-driven self-assembly behind metal-organic materials.Here,we have synthesized a triangular metal-organic polygon(MOT-1),assembled from bulky tetramethyl terephthalate and Zr-based secondary building unit.Surprisingly,the Zr-based secondary building unit serves as an unusual ditopic Zr-connector,toform metal-organic polygon MOT-1,proven to be a good candidate for water adsorption with recyclability.This study highlights the interplay of the geometrically frustrated ligand and secondary building unit in controlling the connectivity of metal-organic polygon.Such a strategy can be further used to unveil a new class of metal-organic materials.
文摘Diffusion reaction of the labile building block Mg（acacCN）2 （acacCN= 3-cyanoacetylacetonate） with silver salts leads to a series of solvated Mg/Ag bimetallic coordination polymers with composition [Mg（acacCN）aAg].solvent. Despite their common stoichiometry, the topology of these polymers depends on the solvent of crystallization. The two-dimensional coordination compound [Mg（acacCN）aAg]-4CHCl3 in space group P]- is obtained as platelet-shaped crystals from a mixture of methanol and chloroform. When kept in the reaction mixture, these thin plates within one week convert to isometric tetrahedral crystals of the 3D network [Mg（acacCN）3Ag]. 2CHC13 in the cubic space group/9213. The transformation reaction proceeds via dissolution and recrystallization. The co-crystallized solvent molecules play an important role for stabilizing the target structure： They subtend Cl...Cl contacts and interact via non- classical C-H.-. O hydrogen bonds with the coordination framework. In the new cubic coordination network, both Mg（II） and Ag（I） adopt octahedral coordination, with unprecedented face-sharing by bridging O atoms of three acetylacetonato moieties. Prolonged standing of [Mg（acacCN）3Ag]-2CHCl3 in the reaction medium leads to further degradation, under formation of [Ag（acacCN）].
