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Reactions of two brominated bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), with various organoamines resulted in six supramolecular organic frameworks (SOFs), formulated as (TBBPF2–)2·(HPZ+)2·(H2PZ2+) (1), (TBBPF–)2·(H2PZ2+)·2H2O·2MeOH (2), (TBBPF)·(TBBPF–)·(HDABCO+)·H2O (3), (TBBPF)·(HMTA) (4), (TBBPA)·(HMTA) (5), and (TBBPA)3·(HMTA)3·H2O (6) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine). Compounds 1–6 were characterized by single-crystal and powder X-ray diffractions. The predominant driving forces in 1–6 are hydrogen bonds (H-bonds), by which the compounds assemble into supramolecular organic frameworks with versatile topological structures. Compound 1 contains TBBPF/PZ in a 2:3 ratio and exhibits 2D (two-dimensional) H-bonded supramolecular 44-sql layer structure built by the four-connected {H2PZ2+} moieties and {TBBPF2–}. Compound 2 shows a 2-fold interpenetrated 3D (three-dimensional) H-bonded networks comprised by TBBPF/...

Reactions of two halogenated derivatives of bis(4-hydroxyphenyl)sulphone (BPS, 1), tetrabromobisphenol-S (TBBPS, 2), and tetrachlorobisphenol-S (TCBPS, 3), with piperazine (PZ, 4), were investigated by means of the combinational usage of solvothermal and mechanochemical methods. The resultant organic complexes, [(C6H2OBr2)2SO2]·[(C4H10N2)2CH2] (5), [(C6H2OBr2)2SO2]2·(C4H12N2)2·3(CH3OH) (6), [(C6H2OCl2)2SO2]·[(C4H10N2)2CH2] (7), and [(C6H2OCl2)2SO2]2·(C4H12N2)2·3(CH3OH) (8), were fully characterized by single crystal and powder X-ray diffractions. In the cases of complexes 5 and 7 that were prepared from solvothermal conditions, a rare metal-free in situ ligand formation has been observed, in which the new organic molecule 1,2-bispiperazinylmethane was presumably originated from the double C–N coupling of two piperazines on a carbon atom coming from methanol. In addition, the relevant concomitants 6 and 8 were also isolated from the solutions of 5 and 7, respectively. Complexes 6 and 8 contain 1:1 starting...

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 interactio...

We describe the use of two "bent" molecules, tetrabromobisphcnol-S (2) and 1,3-bis(4-pyridyl)-propane (3), to build an interesting organic cocrystal [(C 6 H 2 OBr 2 ) 2 SO 2 ]·[(C 5 H 4 N) 2 (CH 2 ) 3 ]·MeOH (4). In the molecular structure ot cocrystal 4, the cocrystallizing components (coformers) 2 and 3 assemble into a 1:1 supramolecular adduct featuring unprecedented triple-stranded molecular entanglement, called a "molecular braid". via O-H···N interactions, which is the first example of such one-dimensional entanglement in the realm of organic cocrystals.

A family of inorganic−organic hybrid solid materials has been assembled from presynthesized organic decamethylcucurbit[5]uril (Me10Q[5]) macrocycles and the well-known inorganic polyoxometalate (POM) clusters. Three compounds, formulated as [Na6(H2O)11(Me10Q[5])2]·[β-H2W12O40]·5H2O (1), [Na4(H2O)7(Me10Q[5])2]·[α-SiW12O40]·20H2O (2), and [Na4(H2O)7(Me10Q[5])2]·[β-SiW12O40]·13H2O (3) are reported. In the molecular structures of the three compounds, versatile Keggin-type polyoxotungstate clusters were successfully assembled as inorganic building blocks to build hybrid materials with Me10Q[5]. Compound 1 comprises β-Keggin-type iso-polyoxotungstate [H2W12O40]6− clusters and Me10Q[5]. Compound 2 contains α-Keggin-type [SiW12O40]4− heteropolyanions and Me10Q[5], whereas compound 3 is constructed from β-Keggin-type heteropolyoxosilicotungstate clusters [SiW12O40]4− and Me10Q[5]. All of the compounds feature train-like structural subunits based on central POM/alkali metal backbones and two side rows of parallel M...

To have an insight into the performance of chemically homogeneous but geometrically different isomeric ligands in constructing coordination polymers, two xylene-functionalized N-donors, specifically, p-BIMB and o-BIMB (BIMB = bis-(imidazol-1-ylmethyl)benzene), were treated, in parallel, with CuCN and KI under solvothermal conditions and with CuCl2 and NaN3 in layer diffusion, thereby affording four new coordination polymers with dimensions from 1D to 3D. In particular, the cuprous [Cu2(CN)2(p-BIMB)]n (1) is structured as a 3D framework showing an unprecedented bimodal (8 × 102)(85.10)2 topology and [Cu2(CN)2(o-BIMB)]n (2) as an undulated sheet based on a (CuCN)n network and the cupric {[Cu(N3)2(p-BIMB)2](H2O)2}n (3) is assembled as a 3D polycatenated framework based on the inclined interpenetrating (4,4) nets and [Cu(N3)2(o-BIMB)2]n (4) as a metal-fused ring catenation. The assemblies of 1−4 are of note for revealing a law that the polymers, comparably derived from two isomeric ligands, are similar in met...

A series of complexes constructed from multinuclear copper clusters and polyoxometalates, namely, [Cu6(PO4)2(H2O)2(bpy)6](H3O)2[P2W18O62](bpy=2,2′-bipyridine, 1), [Cu6(PO4)2(H2O)4(phen)6](H2O)2[P2W18O62] (phen = 1,10-phenanthroline, 2), [Cu2Cl(phen)4][PW12O40] (3), [Cu4(HPO4)2(H2O)4(phen)4](H3O)2[PV3W9O40] (4), and [Cu4(HPO4)2(H2O)2(bpy)4](H2O)2[PVW11O40] (5), have been successfully synthesized in situ under hydrothermal conditions via changing the ligand, adjusting the pH value, and introducing low-valence metal (V5+). Complex 1 represents the first example of 1D linear chain constructed from alternating mixed-valence hexacopper (four Cu2+ and two Cu+) clusters and Wells−Dawson type polyoxometalates. Complex 2 exhibits an unprecedented 2D layer network based on hexacopper phosphate and Wells−Dawson type polyoxometalates. Complex 3 constructed from dicopper coordination compounds and Keggin polyoxometalates, was obtained from the similar hydrothermal treatment of 2 at much lower pH value. Complexes 4−5 re...

The smallest members of the cucurbituril family, cucurbit[5]uril and the alkyl-cucurbit[5]urils, can be used as a building blocks, linked by metal ions to create supramolecular rings. The cavities found at the center of these rings have dimensions between 7 and 19 A in width and 8.5 A in depth. The partially substituted alkyl-cucurbit[5]urils present the most interesting supramolecular ring formation. This occurs as a result of selective coordination of metal ions to the carbonyl oxygens of the glycoluril moieties carrying alkyl substitution.

Three new coordination polymers, {[Zn(H2Bpz)(Tph)]·1/2(H2Bpz)}n (1), [Zn2(H2Bpz)(Bpz)(Iph)]n (2), and {[Zn2(H2Bpz)(HBtc)2(H2O)2]·7/6(H2O)}n (3) (H2Bpz = 3,3‘,5,5‘-tetramethyl-4,4‘-bipyrazole; H2Tph = terephthalic acid; H2Iph = isophthalic acid; H3Btc = benzene-1,3,5-tricarboxylic acid), have been isolated from parallel hydrothermal reactions of ZnSO4 and H2Bpz with H2Tph, H2Iph, and H3Btc, respectively. These crystalline solids have been structurally defined, of which 1 was revealed to construct in a 3D architecture with porosity. Interestingly, because of its large porosity, 1 allows the concurrent 2-fold interpenetration and inclusion of free H2Bpz as guest molecule. In contrast to 1, polymer 2 structures in a 2D framework of note for containing both neutral and deprotonated H2Bpz as μ2-and μ4-bridging linkers, respectively. This case demonstrates a rare usage of H2Bpz as ligand in the construction of MOFs. The partial deprotonation of H2Bpz may be a consequence of less acidity of H2Iph than H2Tph, by w...

A novel compound constructed from alternating Wells−Dawson POMs building blocks and mixed-valence hexacopper phosphate cations was isolated and the compound is a 1D infinitely linear chain exhibiting an −ACACAC− type structure.