Heteroligand Molecular “Stirrups” Using Conformationally Flexible Ditopic Pyridyl−Pyrazolyl Ligands

Heteroligand molecular “stirrups” form by the self-assembly of flexible ditopic ligands in combination with 4,4′-bipyridine and [(dppp)Pd)]2+. Crystallographic analysis shows that the ligands, bis[3-(4-pyridyl)pyrazolyl]-m-xylene (mXy4py3pz) and bis[4-(4-pyridyl)pyrazolyl]-p-xylene (pXy4py4pz) form complexes of the type [{(dppp)Pd}2(4,4′-bipy)(L)]·4OTf (1·4OTf and 2·4OTf, respectively) in the solid state, with remarkably similar structures considering the differences in substitution patterns between the two ligands. The self-assembly of both 14+ and 24+ is assisted by face-to-face π interactions on the exterior of the macrocycle between the phenyl rings of the dppp ligands and the pyridyl groups of the ditopic ligands

Ag(I) Organometallic Coordination Polymers and Capsule with Tris-Allyl Cyclotriveratrylene Derivatives

Tris-allyl-cyclotriguaiacylene combines with silver salts to give a range of crystalline network structures and one discrete complex. A number of different coordination modes are found within the complexes including η2-allyl, aryl, and OR groups binding to Ag(I). AgSbF6 gives two types of three-dimensional (3-D) coordination polymer with unusual topologies, along with a discrete Ag2L2 capsule dependent on reaction stoichiometry and reaction conditions. Isostructural coordination chain structures are found with AgBF4 and AgClO4, while use of Ag(CF3SO3) gives two-dimensional (2-D) and 3-D coordination polymers through bridging triflate anions

Ag(I) Organometallic Coordination Polymers and Capsule with Tris-Allyl Cyclotriveratrylene Derivatives

Tris-allyl-cyclotriguaiacylene combines with silver salts to give a range of crystalline network structures and one discrete complex. A number of different coordination modes are found within the complexes including η2-allyl, aryl, and OR groups binding to Ag(I). AgSbF6 gives two types of three-dimensional (3-D) coordination polymer with unusual topologies, along with a discrete Ag2L2 capsule dependent on reaction stoichiometry and reaction conditions. Isostructural coordination chain structures are found with AgBF4 and AgClO4, while use of Ag(CF3SO3) gives two-dimensional (2-D) and 3-D coordination polymers through bridging triflate anions

Heteroligand Molecular “Stirrups” Using Conformationally Flexible Ditopic Pyridyl−Pyrazolyl Ligands

Heteroligand molecular “stirrups” form by the self-assembly of flexible ditopic ligands in combination with 4,4′-bipyridine and [(dppp)Pd)]2+. Crystallographic analysis shows that the ligands, bis[3-(4-pyridyl)pyrazolyl]-m-xylene (mXy4py3pz) and bis[4-(4-pyridyl)pyrazolyl]-p-xylene (pXy4py4pz) form complexes of the type [{(dppp)Pd}2(4,4′-bipy)(L)]·4OTf (1·4OTf and 2·4OTf, respectively) in the solid state, with remarkably similar structures considering the differences in substitution patterns between the two ligands. The self-assembly of both 14+ and 24+ is assisted by face-to-face π interactions on the exterior of the macrocycle between the phenyl rings of the dppp ligands and the pyridyl groups of the ditopic ligands

Coordination Polymers Utilizing <i>N</i>‑Oxide Functionalized Host Ligands

Pyridyl functionalized host molecules are oxidized to their <i>N</i>-oxide analogues and form a series of coordination polymers and discrete complexes with transition metal cations. Complex {[Ag₃(NMP)₆(L1)₂]·3­(ClO₄)}_∞ where L1 = tris­(isonicotinoyl-<i>N</i>-oxide)­cyclotriguaiacylene, NMP = <i>N</i>-methylpyrrolidone, is a three-dimensional (3-D) 3,6-connected coordination polymer of pyrite-like (pyr) topology and features ligand unsupported argentophilic interactions, while two-dimensional (2-D) 3,6-connected coordination polymers with the rarely reported kagome dual (kgd) topology are found for [M­(L1)₂]²⁺ where M = Zn, Cd, Cu. Ligand L2 = tris­(nicotinoyl-<i>N</i>-oxide)­cyclotriguaiacylene forms a 2-D coordination polymer with 4⁴ (sql) grid topology in complexes {[M­(L2)₂(DMF)₂]·2ClO₄·8­(DMF)}_∞ M = Cd or Cu, DMF = <i>N,N</i>′-dimethylformamide, and a double-linked chain structure in {[Co­(L2)₂(DMF)₂]·2NO₃·4­(DMF)·H₂O}_∞, and both types of structure feature hand-shake self-inclusion motifs either within or between the polymers. 2-D coordination networks with 6³ (hcb) topologies are found in complexes {[M­(L3)­(NO₃)₂]·2­(DMF)}_∞ (M = Cd, Zn) and {[Cu₅(L3)₂Cl₁₀(NMP)₄]}_∞ where L3 = tris­(2-pyridylmethyl)­cyclotriguaiacylene, while [Ag₂(L3)₂(NMP)₄]·2­(BF₄)·2­(NMP) has a discrete dimeric structure which again shows hand-shake host–guest interactions supported by π–π stacking

Self-Assembly of a 3-D Triply Interlocked Chiral [2]Catenane

A tripodal cyclotriveratrylene-based ligand with chelating 2,2‘-bipyridine arms self-assembles with either Zn(NO3)2 or Co(NO3)2 to give 3-D trigonal bipyramidal [M3L2] cage assemblies. These cages triply interlock forming [2]catenane species that have been characterized by mass spectrometry and, in the case of the Zn(II) complex, by X-ray crystallography

Self-Assembly of a 3-D Triply Interlocked Chiral [2]Catenane

A tripodal cyclotriveratrylene-based ligand with chelating 2,2‘-bipyridine arms self-assembles with either Zn(NO3)2 or Co(NO3)2 to give 3-D trigonal bipyramidal [M3L2] cage assemblies. These cages triply interlock forming [2]catenane species that have been characterized by mass spectrometry and, in the case of the Zn(II) complex, by X-ray crystallography

Coordination Polymers Utilizing <i>N</i>‑Oxide Functionalized Host Ligands

Pyridyl functionalized host molecules are oxidized to their <i>N</i>-oxide analogues and form a series of coordination polymers and discrete complexes with transition metal cations. Complex {[Ag₃(NMP)₆(L1)₂]·3­(ClO₄)}_∞ where L1 = tris­(isonicotinoyl-<i>N</i>-oxide)­cyclotriguaiacylene, NMP = <i>N</i>-methylpyrrolidone, is a three-dimensional (3-D) 3,6-connected coordination polymer of pyrite-like (pyr) topology and features ligand unsupported argentophilic interactions, while two-dimensional (2-D) 3,6-connected coordination polymers with the rarely reported kagome dual (kgd) topology are found for [M­(L1)₂]²⁺ where M = Zn, Cd, Cu. Ligand L2 = tris­(nicotinoyl-<i>N</i>-oxide)­cyclotriguaiacylene forms a 2-D coordination polymer with 4⁴ (sql) grid topology in complexes {[M­(L2)₂(DMF)₂]·2ClO₄·8­(DMF)}_∞ M = Cd or Cu, DMF = <i>N,N</i>′-dimethylformamide, and a double-linked chain structure in {[Co­(L2)₂(DMF)₂]·2NO₃·4­(DMF)·H₂O}_∞, and both types of structure feature hand-shake self-inclusion motifs either within or between the polymers. 2-D coordination networks with 6³ (hcb) topologies are found in complexes {[M­(L3)­(NO₃)₂]·2­(DMF)}_∞ (M = Cd, Zn) and {[Cu₅(L3)₂Cl₁₀(NMP)₄]}_∞ where L3 = tris­(2-pyridylmethyl)­cyclotriguaiacylene, while [Ag₂(L3)₂(NMP)₄]·2­(BF₄)·2­(NMP) has a discrete dimeric structure which again shows hand-shake host–guest interactions supported by π–π stacking

Octapi Interactions: Self-Assembly of a Pd-Based [2]Catenane Driven by Eightfold π Interactions

Octapi Interactions: Self-Assembly of a Pd-Based [2]Catenane Driven by Eightfold π Interaction

Octapi Interactions: Self-Assembly of a Pd-Based [2]Catenane Driven by Eightfold π Interactions

Octapi Interactions: Self-Assembly of a Pd-Based [2]Catenane Driven by Eightfold π Interaction