In this work,titanium-capped cobalt clathrochelates have been applied as secondary building units(SBUs) fo r the construction of supramolecular rings.Two heterometallic wheel-like [Ti_(6) Co_(12)] complexes based on c...In this work,titanium-capped cobalt clathrochelates have been applied as secondary building units(SBUs) fo r the construction of supramolecular rings.Two heterometallic wheel-like [Ti_(6) Co_(12)] complexes based on cobalt clathrochelates,[C_(6)H_(15)N_(4)]_(2)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(2,Dmg=dimethy[glyoxime) and H_(6)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(3),have been successfully synthesized and characterized.The supramolecular stacking modes of these wheels are largely dependent on the applied synthetic conditions,which further impact their gas adsorption properties.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
General and straightforward synthetic strategy towards the iron(Ⅱ)clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed.Their hexachloro...General and straightforward synthetic strategy towards the iron(Ⅱ)clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed.Their hexachloroclathrochelate precursors were prepared by the direct template condensation of dichloroglyoxime with a suitable boronic acid on the Fe^(2+) ion as a matrix and underwent a stepwise nucleophilic substitution with S_(2)-,N_(2)- or O_(2)-bis-nucleophiles,forming the alicyclic or aromatic N_(2)-,S_(2)-or O_(2)-six-membered fragments.Depending on the reaction conditions and precursor-to-dinucleophile molar ratios,iron(Ⅱ)clathrochelates with one(S,O and N),two(S,O and N)or three(S and O)X_(2)-six-membered ribbed substituent(s)were obtained.Their reactivity substantially decreases in a row:Cl_(6)-Cage>Cl_(4)X_(2)-Cage(where X=S,O or,especially,N)>Cl_(2)X_(4)-Cage(where X=S or O).The reactive monoribbed-functionalized clathrochelates underwent further chemical transformations giving the target macrobicyclic complexes with terminal vector groups.As follows from the single crystal XRD data,their FeN_(6)-coordination polyhedra possess the geometry intermediate between a trigonal prism and a trigonal antiprism(φ=21.3°—25.20°).Fe-N distances vary from 1.887(6)to 1.933(8)Å.Their 3D-molecules,the hydrophobic–hydrophilic balance in which can be tuned using a ribbed functionalization,form in the crystals the intermolecular specific halogen bonds and/or hydrophobic interactions.展开更多
基金supported by the National Natural Science Foundation of China (NSFC,Nos.21673238 and 21922111)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB20000000)。
文摘In this work,titanium-capped cobalt clathrochelates have been applied as secondary building units(SBUs) fo r the construction of supramolecular rings.Two heterometallic wheel-like [Ti_(6) Co_(12)] complexes based on cobalt clathrochelates,[C_(6)H_(15)N_(4)]_(2)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(2,Dmg=dimethy[glyoxime) and H_(6)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(3),have been successfully synthesized and characterized.The supramolecular stacking modes of these wheels are largely dependent on the applied synthetic conditions,which further impact their gas adsorption properties.
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The synthesis of clathrochelate complexes was supported by Russian Science Foundation(project 21-73-20145)G.E.Z.also thanks the RFBR(grants 19-33-60047)for the financial support。
文摘General and straightforward synthetic strategy towards the iron(Ⅱ)clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed.Their hexachloroclathrochelate precursors were prepared by the direct template condensation of dichloroglyoxime with a suitable boronic acid on the Fe^(2+) ion as a matrix and underwent a stepwise nucleophilic substitution with S_(2)-,N_(2)- or O_(2)-bis-nucleophiles,forming the alicyclic or aromatic N_(2)-,S_(2)-or O_(2)-six-membered fragments.Depending on the reaction conditions and precursor-to-dinucleophile molar ratios,iron(Ⅱ)clathrochelates with one(S,O and N),two(S,O and N)or three(S and O)X_(2)-six-membered ribbed substituent(s)were obtained.Their reactivity substantially decreases in a row:Cl_(6)-Cage>Cl_(4)X_(2)-Cage(where X=S,O or,especially,N)>Cl_(2)X_(4)-Cage(where X=S or O).The reactive monoribbed-functionalized clathrochelates underwent further chemical transformations giving the target macrobicyclic complexes with terminal vector groups.As follows from the single crystal XRD data,their FeN_(6)-coordination polyhedra possess the geometry intermediate between a trigonal prism and a trigonal antiprism(φ=21.3°—25.20°).Fe-N distances vary from 1.887(6)to 1.933(8)Å.Their 3D-molecules,the hydrophobic–hydrophilic balance in which can be tuned using a ribbed functionalization,form in the crystals the intermolecular specific halogen bonds and/or hydrophobic interactions.
