Alkylation Reactions of [WS₄]^2- and [(η⁵-C₅Me₅)WS₃]^- with 2,6-Bis(bromomethyl)pyridine: The First Isolation of Bisalkylated Tetrathiometalate WS₂{2,6-(SCH₂)₂(C₅H₃N)}

The trithio and tetrathio complexes of tungsten (PPh4)[Cp*WS3] (Cp* = η5-C5Me5) and (PPh4)2[WS4] undergo alkylation reactions with 2,6-bis(bromomethyl)pyridine to yield [(Cp*WS2)2{2,6-(SCH2)2(C5H3N)}]·CH3CN (1·CH3CN) (73.1% yield) and WS2{2,6-(SCH2)2(C5H3N)} (2) (76.0% yield), respectively. In the dinuclear complex 1, two Cp*WS3 units are linked by a 2,6-dimethylenepyridine bridge, and the pyridine nitrogen is not coordinated at tungsten. Complex 2 is the first example of bisalkylated tetrathiometalates, the mononuclear structure of which is stabilized by coordination of the pyridine nitrogen

Anion-Assisted Structural Variation of Cadmium Coordination Polymers: From 2D → 3D Inclined Polycatenation to 2D → 3D Polythreading

Anion-assisted molecular assemblies of two cadmium coordination polymers, based on 44-sql subunits (or (4,4) net) and showing interesting frameworks of 2D → 3D inclined polycatenation and 2D → 3D polythreading, respectively, are reported

Anion-Assisted Structural Variation of Cadmium Coordination Polymers: From 2D → 3D Inclined Polycatenation to 2D → 3D Polythreading

Anion-assisted molecular assemblies of two cadmium coordination polymers, based on 44-sql subunits (or (4,4) net) and showing interesting frameworks of 2D → 3D inclined polycatenation and 2D → 3D polythreading, respectively, are reported

Effects of Cocrystalline Subunits on the Supramolecular Chemistry of Me₁₀Q[5]: From Simple Inorganic Anions to Cluster Anions

Five supramolecular assemblies, formulated as {K2(H2O)3·[(Me10Q[5])@(H2O)0.5]}·Cl2 1, [K2(H2O)2·(Me10Q[5]@H2O)](ClO4)2·H2O 2, {K(H2O)·K(H2O)(SCN)Me10Q[5]}·(SCN)·H2O 3, [Na2(H2O)2K2(H2O)4(Me10Q[5])]·[Mo8O26] 4 and [Na2(H2O)2Rb2(H2O)4(Me10Q[5])]·[Mo8O26] 5, have been successfully isolated. Compounds 1−5 exhibit various structures based on the coordination of Me10Q[5] with alkali metals controlled by a series of anions, in which the anions play multiple roles of coordination, space-filling, charge-compensating etc. In the structure of compound 1, Me10Q[5] is capped by two [K(H2O)2]+ moieties through the carbonyl O atoms on the portals to form a bicapped unit. The bicapped Me10Q[5] units are interconnected to form a covalent bonded chain structure. Uncoordinated Cl− anions fill in the crystal lattice behaving as both counterions and space-filling agents. Compound 2 possesses isolated bicapped units comprised by Me10Q[5] and [K(H2O)]+ moieties, which are further linked via extensive hydrogen bonding interactions between the coordinated and uncoordinated water molecules into a supramolecular chain structure. The ClO4− anions are involved in the formation of hydrogen bonds with the coordinated aqua ligands located on the supramolecular chains. Compound 3 features an asymmetric bicapped Me10Q[5] unit due to the coordination of a [K(H2O)]+ or [K(H2O)(SCN)]+ on each portal of Me10Q[5]. The bicapped units in 3 are further extended into a supramolecular chain structure by hydrogen bonds between the coordinated water and carbonyl O atoms of Me10Q[5]. Moreover, uncoordinated SCN− anions are also observed in the crystal lattice. Compounds 4 and 5 are isomorphous and display interesting 3D network structures built by the interconnections of Me10Q[5], mixed alkali metal cations (Na+/K+ for 4 and Na+/Rb+ for 5), and [α-Mo8O26]4− cluster anions. In this study, the supramolecular assemblies of Me10Q[5] based solids show an anion dependent feature, which is systematically explored

Anion-Assisted Structural Variation of Cadmium Coordination Polymers: From 2D → 3D Inclined Polycatenation to 2D → 3D Polythreading

Anion-assisted molecular assemblies of two cadmium coordination polymers, based on 44-sql subunits (or (4,4) net) and showing interesting frameworks of 2D → 3D inclined polycatenation and 2D → 3D polythreading, respectively, are reported

Three-Dimensional Pillared-Layer 3d-4f Heterometallic Coordination Polymers With or Without Halides

Hydrothermal reactions of isonicotinic acid (Hina) and hemimellitic acid (H3hma) with lanthanide oxides and copper halides yielded 10 three-dimensional (3D) pillared-layer 3d-4f heterometallic coordination polymers (HCPs) with three structural types. They are formulated as [Ln2Cu2(μ2-X)­(hma)­(ina)4(H2O)2]n·2nH2O [Ln = La, X = Cl (I-A), Ln = La, X = Br (I-B), Ln = La, X = I (I-C), Ln = Nd, X = Cl (I-D), Ln = Nd, X = Br (I-E)], [Ln3Cu4.5I3.5(μ3-OH)­(hma)­(ina)6(H2O)]n·nH2O [Ln = Pr (II-A), Nd­(II-B)], and [LnCu0.5(hma)­(ina)­(H2O)]n·nH2O [Ln = La (III-A), Ce (III-B), Pr (III-C)]. All the HCPs are characterized by single-crystal X-ray diffractions. In type I structures, Ln-organic layers are pillared by halide-bridged dinuclear [Cu2(μ2-Cl)­(ina)4] units through Ln–O bonds. In type II structures, Ln-organic layers are pillared by two different kinds of monovalent Cu-based building units, namely, halide-free [Cu­(ina)2] and halide-containing [Cu8(μ3-I)6(μ4-I)­(ina)10]n. In type III structures, undulate heterometallic Cu­(II)–Ln­(III) layers are pillared by organic ina ligands via Ln–O and Cu–N bonds. The solid-state photoluminescent properties of I-D and II-B were also investigated at room temperature

Effects of Cocrystalline Subunits on the Supramolecular Chemistry of Me₁₀Q[5]: From Simple Inorganic Anions to Cluster Anions

Five supramolecular assemblies, formulated as {K2(H2O)3·[(Me10Q[5])@(H2O)0.5]}·Cl2 1, [K2(H2O)2·(Me10Q[5]@H2O)](ClO4)2·H2O 2, {K(H2O)·K(H2O)(SCN)Me10Q[5]}·(SCN)·H2O 3, [Na2(H2O)2K2(H2O)4(Me10Q[5])]·[Mo8O26] 4 and [Na2(H2O)2Rb2(H2O)4(Me10Q[5])]·[Mo8O26] 5, have been successfully isolated. Compounds 1−5 exhibit various structures based on the coordination of Me10Q[5] with alkali metals controlled by a series of anions, in which the anions play multiple roles of coordination, space-filling, charge-compensating etc. In the structure of compound 1, Me10Q[5] is capped by two [K(H2O)2]+ moieties through the carbonyl O atoms on the portals to form a bicapped unit. The bicapped Me10Q[5] units are interconnected to form a covalent bonded chain structure. Uncoordinated Cl− anions fill in the crystal lattice behaving as both counterions and space-filling agents. Compound 2 possesses isolated bicapped units comprised by Me10Q[5] and [K(H2O)]+ moieties, which are further linked via extensive hydrogen bonding interactions between the coordinated and uncoordinated water molecules into a supramolecular chain structure. The ClO4− anions are involved in the formation of hydrogen bonds with the coordinated aqua ligands located on the supramolecular chains. Compound 3 features an asymmetric bicapped Me10Q[5] unit due to the coordination of a [K(H2O)]+ or [K(H2O)(SCN)]+ on each portal of Me10Q[5]. The bicapped units in 3 are further extended into a supramolecular chain structure by hydrogen bonds between the coordinated water and carbonyl O atoms of Me10Q[5]. Moreover, uncoordinated SCN− anions are also observed in the crystal lattice. Compounds 4 and 5 are isomorphous and display interesting 3D network structures built by the interconnections of Me10Q[5], mixed alkali metal cations (Na+/K+ for 4 and Na+/Rb+ for 5), and [α-Mo8O26]4− cluster anions. In this study, the supramolecular assemblies of Me10Q[5] based solids show an anion dependent feature, which is systematically explored

Effects of Cocrystalline Subunits on the Supramolecular Chemistry of Me₁₀Q[5]: From Simple Inorganic Anions to Cluster Anions

Five supramolecular assemblies, formulated as {K2(H2O)3·[(Me10Q[5])@(H2O)0.5]}·Cl2 1, [K2(H2O)2·(Me10Q[5]@H2O)](ClO4)2·H2O 2, {K(H2O)·K(H2O)(SCN)Me10Q[5]}·(SCN)·H2O 3, [Na2(H2O)2K2(H2O)4(Me10Q[5])]·[Mo8O26] 4 and [Na2(H2O)2Rb2(H2O)4(Me10Q[5])]·[Mo8O26] 5, have been successfully isolated. Compounds 1−5 exhibit various structures based on the coordination of Me10Q[5] with alkali metals controlled by a series of anions, in which the anions play multiple roles of coordination, space-filling, charge-compensating etc. In the structure of compound 1, Me10Q[5] is capped by two [K(H2O)2]+ moieties through the carbonyl O atoms on the portals to form a bicapped unit. The bicapped Me10Q[5] units are interconnected to form a covalent bonded chain structure. Uncoordinated Cl− anions fill in the crystal lattice behaving as both counterions and space-filling agents. Compound 2 possesses isolated bicapped units comprised by Me10Q[5] and [K(H2O)]+ moieties, which are further linked via extensive hydrogen bonding interactions between the coordinated and uncoordinated water molecules into a supramolecular chain structure. The ClO4− anions are involved in the formation of hydrogen bonds with the coordinated aqua ligands located on the supramolecular chains. Compound 3 features an asymmetric bicapped Me10Q[5] unit due to the coordination of a [K(H2O)]+ or [K(H2O)(SCN)]+ on each portal of Me10Q[5]. The bicapped units in 3 are further extended into a supramolecular chain structure by hydrogen bonds between the coordinated water and carbonyl O atoms of Me10Q[5]. Moreover, uncoordinated SCN− anions are also observed in the crystal lattice. Compounds 4 and 5 are isomorphous and display interesting 3D network structures built by the interconnections of Me10Q[5], mixed alkali metal cations (Na+/K+ for 4 and Na+/Rb+ for 5), and [α-Mo8O26]4− cluster anions. In this study, the supramolecular assemblies of Me10Q[5] based solids show an anion dependent feature, which is systematically explored

Effects of Cocrystalline Subunits on the Supramolecular Chemistry of Me₁₀Q[5]: From Simple Inorganic Anions to Cluster Anions

Five supramolecular assemblies, formulated as {K2(H2O)3·[(Me10Q[5])@(H2O)0.5]}·Cl2 1, [K2(H2O)2·(Me10Q[5]@H2O)](ClO4)2·H2O 2, {K(H2O)·K(H2O)(SCN)Me10Q[5]}·(SCN)·H2O 3, [Na2(H2O)2K2(H2O)4(Me10Q[5])]·[Mo8O26] 4 and [Na2(H2O)2Rb2(H2O)4(Me10Q[5])]·[Mo8O26] 5, have been successfully isolated. Compounds 1−5 exhibit various structures based on the coordination of Me10Q[5] with alkali metals controlled by a series of anions, in which the anions play multiple roles of coordination, space-filling, charge-compensating etc. In the structure of compound 1, Me10Q[5] is capped by two [K(H2O)2]+ moieties through the carbonyl O atoms on the portals to form a bicapped unit. The bicapped Me10Q[5] units are interconnected to form a covalent bonded chain structure. Uncoordinated Cl− anions fill in the crystal lattice behaving as both counterions and space-filling agents. Compound 2 possesses isolated bicapped units comprised by Me10Q[5] and [K(H2O)]+ moieties, which are further linked via extensive hydrogen bonding interactions between the coordinated and uncoordinated water molecules into a supramolecular chain structure. The ClO4− anions are involved in the formation of hydrogen bonds with the coordinated aqua ligands located on the supramolecular chains. Compound 3 features an asymmetric bicapped Me10Q[5] unit due to the coordination of a [K(H2O)]+ or [K(H2O)(SCN)]+ on each portal of Me10Q[5]. The bicapped units in 3 are further extended into a supramolecular chain structure by hydrogen bonds between the coordinated water and carbonyl O atoms of Me10Q[5]. Moreover, uncoordinated SCN− anions are also observed in the crystal lattice. Compounds 4 and 5 are isomorphous and display interesting 3D network structures built by the interconnections of Me10Q[5], mixed alkali metal cations (Na+/K+ for 4 and Na+/Rb+ for 5), and [α-Mo8O26]4− cluster anions. In this study, the supramolecular assemblies of Me10Q[5] based solids show an anion dependent feature, which is systematically explored

Effects of Cocrystalline Subunits on the Supramolecular Chemistry of Me₁₀Q[5]: From Simple Inorganic Anions to Cluster Anions

Five supramolecular assemblies, formulated as {K2(H2O)3·[(Me10Q[5])@(H2O)0.5]}·Cl2 1, [K2(H2O)2·(Me10Q[5]@H2O)](ClO4)2·H2O 2, {K(H2O)·K(H2O)(SCN)Me10Q[5]}·(SCN)·H2O 3, [Na2(H2O)2K2(H2O)4(Me10Q[5])]·[Mo8O26] 4 and [Na2(H2O)2Rb2(H2O)4(Me10Q[5])]·[Mo8O26] 5, have been successfully isolated. Compounds 1−5 exhibit various structures based on the coordination of Me10Q[5] with alkali metals controlled by a series of anions, in which the anions play multiple roles of coordination, space-filling, charge-compensating etc. In the structure of compound 1, Me10Q[5] is capped by two [K(H2O)2]+ moieties through the carbonyl O atoms on the portals to form a bicapped unit. The bicapped Me10Q[5] units are interconnected to form a covalent bonded chain structure. Uncoordinated Cl− anions fill in the crystal lattice behaving as both counterions and space-filling agents. Compound 2 possesses isolated bicapped units comprised by Me10Q[5] and [K(H2O)]+ moieties, which are further linked via extensive hydrogen bonding interactions between the coordinated and uncoordinated water molecules into a supramolecular chain structure. The ClO4− anions are involved in the formation of hydrogen bonds with the coordinated aqua ligands located on the supramolecular chains. Compound 3 features an asymmetric bicapped Me10Q[5] unit due to the coordination of a [K(H2O)]+ or [K(H2O)(SCN)]+ on each portal of Me10Q[5]. The bicapped units in 3 are further extended into a supramolecular chain structure by hydrogen bonds between the coordinated water and carbonyl O atoms of Me10Q[5]. Moreover, uncoordinated SCN− anions are also observed in the crystal lattice. Compounds 4 and 5 are isomorphous and display interesting 3D network structures built by the interconnections of Me10Q[5], mixed alkali metal cations (Na+/K+ for 4 and Na+/Rb+ for 5), and [α-Mo8O26]4− cluster anions. In this study, the supramolecular assemblies of Me10Q[5] based solids show an anion dependent feature, which is systematically explored