Hai-Yan Chen

A series of novel entangled coordination frameworks with inherent features of self-threading, polyrotaxane and polycatenane

Self-assembly of transition metal salts with long aromatic dicarboxylate ligands and N-containing ligands affords a series of entangled coordination frameworks based on different metal cores, namely [Mn4(μ2-OH2)2(sdba)4(bpp)4] (1), [Mn2(sdba)2(btb)0.5(H2O)] (2), [Mn4(sdba)4(bim)(H2O)4]·2H2O (3), [Ni(sdba)(bim)(H2O)2]·2H2O (4), [Co3(sdba)2(Hsdba)2(2,2′-bpy)2] (5) and [Ni2(bpda)2(bim)2]·H2O (6) (H2sdba = 4,4′-sulfonyldibenzoic acid, H2bpda = 4,4′-carbonyldibenzoic acid, bpp = 1,3-bis(4-pyridyl)propane, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bim = 1,4-bis(imidazol-1-yl)butane, 2,2′-bpy = 2,2′-bipyridine). Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Compound 1 is a peculiar 2D self-threading network containing unusual triflexural helical motifs, which can be rationalized as a 6-connected 2D 36-hxl (hexagonal lattice) net with double edges. Compound 2 represents the first example of a 2D polycatenated framework formed by 1D quadruple chains, which could be considered as formed by interconnected 1D polyrotaxane columns involving the unusual [3]rotaxane components. Compound 3 consists of two interlocked 2D cage-containing frameworks and exhibits an unusual (2D → 2D) parallel interpenetrating array with coexistence of polyrotaxane and polycatenane. Compound 4 is composed of two interpenetrating 2D loop-containing frameworks with 4-connected (2.65) topology, and it can also be considered as being constructed by interconnected parallel 1D polyrotaxane chains. Compound 5 is comprised of two identical 2D hydrogen-bonded layers with 6-connected (22.48.65) topology that are interpenetrated in a parallel fashion, resulting in a twofold interpenetrating net having both polyrotaxane and polycatenane characters. Compound 6 represents an unusual mode of interpenetration of two distinct 3D frames both with CdSO4 topology, which is still very rare in entangled systems. In addition, the magnetic properties of compounds 1, 3, 4, 5 and 6 are discussed.

An unprecedented (5,12)-connected 3D self-penetrating metal–organic framework based on dinuclear barium clusters as building blocks

An unprecedented binodal (5,12)-connected 3D self-penetrating metal–organic framework was first assembled from dinuclear barium clusters as 12-connected nodes and flexible ligands 4,4′-sulfonyldibenzoate as 5-connected nodes, and it represents the highest connected self-penetrating topology presently known for metal–organic frameworks.

Unusual self-threading and interdigitated architectures self-assembled from long flexible ligands and d10 metal salts

Four new entangled metal–organic polymers, namely [Cd2(sdba)2(Htpim)2(H2O)2]·5H2O (1), [Zn(sdba)(Htpim)] (2), [Cd(sdba)(bim)] (3), [Cd(sdba)(bimp)] (4) (sdba = 4,4′-sulfonyldibenzoate, Htpim = 2,4,5-tri(4-pyridyl)-imidazole, bim = 1,4-bis(imidazol-1-yl)butane, bimp = 1,4-bis(imidazol-1-yl)propane), have been hydrothermally synthesized and further characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectra and TG analyses. Compound 1 consists of two identical 3D self-threading frameworks with CdSO4 topology, which exhibits a twofold interpenetrating architecture and represents the first entangled coordination polymer containing both interpenetration and self-threading features. Compound 2 exhibits a novel (1D → 3D) interdigitated architecture that is obtained from the self-assembly of 1D tubelike structures, in which each 1D tube is interdigitated by dangling arms from four adjacent tubes belonging to four different spatial orientations. Compounds 3 and 4 are close to being isostructural, and both exhibit a novel (2D → 3D) interdigitated architecture, which is assembled from hydrogen-bonded bilayer motifs that are formed by two kinds of chiral layers (one left-handed and the other right-handed) showing a deep mutual interdigitation. In addition, photoluminescent properties for 1–3 are investigated in detail.

Guest-induced expanding and shrinking porous modulation based on interdigitated metal–organic frameworks constructed by 4,4′-sulfonyldibenzoate and barium ions

A series of barium-4,4′-sulfonyldibenzoate (sdba) coordination polymers, namely, [Ba(μ2-OH2)(sdba)(H2O)3]·0.5H2O (1), [Ba(μ2-OH2)(sdba)(H2O)3]·0.5ben·H2O (2), [Ba(μ2-OH2)(sdba)(H2O)3]·0.5tolu·H2O (3), [Ba(μ2-OH2)(sdba)(H2O)3]·0.5bpy·H2O (4), [Ba(μ2-OH2)(sdba)(H2O)3]·0.25bim·H2O (5), [Ba(μ2-OH2)(sdba)(H2O)3]·0.5dfb·0.25H2O (6) and [Ba(μ2-OH2)(sdba)(H2O)3]·3.5H2O (7) (ben = benzene, tolu = toluene, bpy = 2,2′-bipyridine, bim = 1,4-bis(imidazol-1-yl)butane, dfb = 1,3-difluoro-benzene (a fragment of fluconazole)), have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectra, and TG analyses. Compounds 1–7 are built upon similar sidearm-containing 2D bilayer motifs, and the adjacent layers are stacked in a mutual interdigitation, such that channels are created. The channels form a hydrogen-bonded interior for guest molecules. In practice, compounds 1 and 7 contain different quantities of free water molecules as guests in the channels, whereas compounds 2–6 contain ben, tolu, bpy, bim and dfb molecules as well as free water molecules in their channels, respectively. The different interlayer distances and free void spaces of 1–7 indicate the effect of guest-induced expanding and shrinking porous modulation, and give a clue to the dynamic arrangement in this system. This indicates the obtained compounds (1–7) are categorized as a member of a new generation of compounds tending towards functional porous coordination polymers. In addition, the photoluminescent properties for all the compounds (1–7) were investigated in detail.

Helicity controlled by the chirality of amino acid: two novel enantiopure chiral 3D architectures containing fivefold interwoven helices

Two novel three-dimensional (3D) chiral coordination polymers, namely [Zn4(btc)2(Hbtc)(L-His)2(H2O)4]·1.5H2O (L-1) and [Zn4(btc)2(Hbtc)(D-His)2(H2O)4]·1.5H2O (D-1), have been assembled from zinc salt with mixed ligands 1,3,5-benzenetricarboxylic acid (H3btc) and chiral histidine (His). Their structures were determined by single-crystal X-ray diffraction analyses, elemental analyses, infrared (IR) spectra, X-ray powder diffraction, circular dichroism (CD) spectra, and thermogravimetric (TG) analysis. Compounds L-1 and D-1 are enantiomers and exhibit unique 3D chiral frameworks containing fivefold interwoven helices, which represent the first examples of chiral metal–amino acid complexes containing n-fold interwoven helices. Furthermore, the helices in L-1 are left-handed, while those in D-1 are right-handed, which indicate that the handedness of helices can be controlled by the chirality of His bound to the metal. More wonderfully, the 3D framework can be simplified to a (3,4)-connected chiral net with an unprecedented (4·92)(4·94·11) topology. Moreover, the luminescent properties of compound L-1 are discussed.

An unprecedented 3-fold interpenetrated double-edged pseudo-diamondoid network containing exceptional 5-fold interlocking tri-flexure helices and 15-fold interwoven helices

The first entangled metal-ppa complex, containing unique 5-fold interlocking tri-flexure helices and 15-fold interwoven helices, defines an unprecedented 3-fold interpenetrated double-edged pseudo-diamondoid (pseudo-dia) network, which, not only represents the first and only example of interpenetrating metal-quinolone complex, but also represents the highest degree of interpenetration presently known for double-edged nets.

catena-Poly[[(2,2′-bipyridine)­manganese(II)]-μ3-4,4′-sulfonyl­dibenzoato]

In the title compound, [Mn(C14H8O6S)(C10H8N2)]n, the MnII ion is coordinated by four O atoms from three 4,4′-sulfonyldibenzoate (sdba) ligands and two N atoms from one 2,2′-bipyridine (2,2′-bipy) ligand in a distorted octahedral geometry. The manganese atoms are alternately bridged either by two sdba ligands, with an Mn⋯Mn separation of 12.284 (1) Å, or by two carboxylate groups from two sdba ligands, with an Mn⋯Mn separation of 4.064 (1) Å, thus producing polymeric chains propagated in [101]. Weak intermolecular C—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distance of 3.730 (3) Å between the aromatic rings of neighbouring polymeric chains] further stabilize the crystal packing.

4-(3-Carb-oxy-1-ethyl-6-fluoro-4-oxo-1,4-dihydroquinolin-7-yl)piperazin-1-ium 4-carb-oxy-benzoate-benzene-1,4-dicarb-oxy-lic acid (2/1).

In the title compound, C16H19FN3O3 +·C8H5O4 −·0.5C8H6O4, the benzene-1,4-dicarboxylic acid molecule is located on a centre of symmetry. In the crystal, the molecules and ions are connected by intermolecular C—H⋯O and O—H⋯O hydrogen bonds and π–π stacking interactions [with a centroid–centroid distance of 3.402 (2) Å], generating a three-dimensional supramolecular structure.

Bis(2-carboxybenzo-ato-κO)bis-[1-cyclo-propyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-dihydro-quinoline-3-carboxyl-ato-κO,O]manganese(II) dihydrate.

The title compound, [Mn(C17H18FN3O3)2(C8H5O4)2]·2H2O or [Mn(cfH)2(1,2-Hbdc)2]·2H2O (cfH = ciprofloxacin = 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid, 1,2-bdc = benzene-1,2-dicarboxylate), has been prepared under hydrothermal conditions. The Mn2+ atom, located on an inversion centre, exhibits a distorted octahedral geometry, coordinated by four O atoms from two symmetry-related zwitterionic ciprofloxacin ligands in the equatorial positions and two O atoms of two 1,2-Hbdc ligands in the axial positions. The complex molecules are linked into a two-dimensional network through N—H⋯O and OW—H⋯O hydrogen bonds. A strong intramolecular hydrogen bond between the carboxyl/carboxylate groups of the 1,2-Hbdc anion is also present. The layers are further extended through off-set aromatic π–π stacking interactions of cfH groups [centroid–centroid distance of 3.657 (2) Å] into the final three-dimensional supramolecular arrays.

Diaqua-bis-[8-ethyl-5-oxo-2-(piperazin-4-ium-1-yl)-5,8-dihydro-pyrido[2,3-d]pyrimidine-6-carboxyl-ato]copper(II) bis[4-(4-carboxyphenoxy)benzoate].

In the title compound, [Cu(C14H17N5O3)2(H2O)2](C14H9O5)2, the Cu2+ atom, located on an inversion centre, exhibits a distorted octahedral geometry, coordinated by four O atoms from two pipemidic acid ligands in equatorial positions and two water molecules in axial positions. The pipemidic acid ligand acts a bidentate ligand and the single deprotonated 4,4′-oxydibenzoic acid acts as an anion. Classical N—H⋯O and O—H⋯O hydrogen bonds are present in the crystal structure.