This review (over 380 references) summarizes metal–organic frameworks (MOFs), Materials Institute Lavoisier (MILs), iso-reticular metal–organic frameworks (IR-MOFs), porous coordination networks (PCNs), zeolitic metal–organic frameworks (ZMOFs) and porous coordination polymers (PCPs) with selected examples of their structures, concepts for linkers, syntheses, post-synthesis modifications, metal nanoparticle formations in MOFs, porosity and zeolitic behavior for applications in gas storage for hydrogen, carbon dioxide, methane and applications in conductivity, luminescence and catalysis.

MOFs, MILs and more: concepts, properties and applications for porous coordination networks (PCNs)

The articles published in the tenth anniversary issue of CrystEngComm are reviewed. The issue highlighted the state-of-the-art of crystal engineering and new trends and developing areas in crystal engineering. In particular, the following article emphasises developments in the areas of intermolecular interactions, notably hydrogen and halogen bonds; metal–organic frameworks or coordination polymers; polymorphism and solvates.

Recent advances in crystal engineering

To determine the influence of reaction conditions on the formation of metal−organic frameworks, a series of Co(II)/H2tbip/bpp complexes, {[Co2(tbip)2(H2O)6]·8H2O}n (1), {[Co(tbip)(bpp)(H2O)]2·4H2O}n (2), {[Co(tbip)(bpp)]·H2O}n (3), {[Co2(H2O)(tbip)(Htbip)2(bpp)2]·0.5(H2tbip)·0.5H2O}n (4), {[Co3(OH)(tbip)2(Htbip)(bpp)]}n (5) (H2tbip = 5-tert-butyl isophthalic acid, bpp = 1,3-bi(4-pyridyl)propane), have been synthesized through the hydrothermal reaction of cobalt(II) acetate, H2tbip, and bpp under different temperatures and pH conditions. The diverse product structures show the marked sensitivity of the structural chemistry of the aromatic carboxylate ligand to synthesis conditions. Polymer 1, which features a three-dimensional (3D) framework with CdSO4 topology, has carboxylate bridging polymeric chains spanning two different directions and bridging water molecules between these chains, and is formed at pH = 4 at 120 °C. At pH = 6, a one-dimensional tube-like structure of 2 is formed. Further increase of t...

Structural Variation from 1D to 3D: Effects of Temperature and pH Value on the Construction of Co(II)-H2tbip/bpp Mixed Ligands System

Five new MnII coordination polymers, namely [Mn2(tbip)2(bix)] (1), [Mn3(tbip)3(bix)2] (2), [Mn3(tbip)2(Htbip)2(bib)2]·4H2O (3), [Mn4(tbip)4(bbp)2(H2O)2] (4), and [Mn4(tbip)4(bip)]·2H2O (5), were prepared by hydrothermal reactions of Mn(II) acetate with H2tbip (5-tert-butyl isophthalic acid) in the presence of different di-imidazolyl coligands (bix =1,4-bis(imidazol-1-ylmethyl)benzene, bib =1,4-bis(imidazol) butane, bbp =1,3-bis(benzimidazol)propane, bip =1,3-bis(imidazol)propane). All complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, single-crystal X-ray crystallography, and powder X-ray diffraction. Single crystal X-ray studies show that these coordination polymers contain homometallic clusters varying from dimeric, trimeric, and tetrameric motifs to polymeric chains depending upon the coligands used. Complex 1 has a 3D 6-connected polycatenane network with dinuclear [Mn2O2] secondary building units. Complex 2 possesses a 3D 8-connected structure with trinuclear ...

MnII Coordination Polymers Based on Bi-, Tri-, and Tetranuclear and Polymeric Chain Building Units: Crystal Structures and Magnetic Properties

A series of structurally diverse metal–organic frameworks (MOFs), [Co4(TPOM)2(L1)4(H2O)4]·H2O (1), [Ni2(TPOM)(L2)2(H2O)2]·2H2O (2), [Co2(TPOM)(L2)2(H2O)2]·H2O (3), [Cu4(TPOM)2(L3)4]·3H2O (4), [Co2(TPOM)0.5(L4)] (5), and [Cd(TPOM)(L3)3]·7H2O (6), where TPOM = tetrakis(4-pyridyloxymethylene)methane, H2L1 = 1,3-benzenedicarboxylic acid, H2L2 = 5-hydroxyisophthalic acid, H3L3 = 1,3,5-benzenetricarboxylic acid, and H4L4 = 1,2,4,5-benzenetetracarboxylic acid, have been hydrothermally synthesized. These complexes were structurally characterized by X-ray diffraction analyses and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Compound 1 shows a 3D 4-connected framework with a rare (84·62) topology. Compounds 2 and 3 are isostructural and display 3D 2-fold interpenetrating frameworks with (64·82)(66)2 topologies. Compound 4 exhibits a 2-fold interpenetrating structure with a scarce trinodal (3,4,5)-connected (4·62)(4·69)66 to...

A Series of 2D and 3D Metal–Organic Frameworks Based on a Flexible Tetrakis(4-pyridyloxymethylene)methane Ligand and Polycarboxylates: Syntheses, Structures, and Photoluminescent Properties

Five new Mn(II) metal–organic coordination polymers, [Mn(tbip)(bipy)]n (1), {[Mn(tbip)(dpe)]·1.5H2O}n (2), [Mn(tbip)(bpa)]n (3), [Mn(mip)(bpa)]n (4) and {[Mn3(mip)2(Hmip)2(bpp)2(H2O)2]·2H2O}n (5), were prepared through hydrothermal reactions of Mn(II) acetate with H2tbip (H2tbip = 5-tert-butyl isophthalic acid) or H2mip (H2mip = 5-methylisophthalic acid) in the presence of different dipyridyl co-ligands (bipy = 4,4′-bipyridine, dpe = 1,2-bi(4-pyridyl)ethene, bpa = 1,2-bi(4-pyridyl)ethane and bpp = 1,3-di(4-pyridyl)propane). All these compounds were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. The structures of 1 and 2 are constructed of [Mn2(tbip)2]n layers, which consist of alternate left- and right-handed helical chains, and further pillared by bipy or dpe ligands into a 3D porous framework. Interestingly, there are two different sizes of pores in 1 and 2. From the topology point of view, both complexes 1 and 2 exhibit the rare rob network based on the dimeric [Mn(COO)]2 subunits as the 6-connected nodes. The ribbon-like chains having 8- and 16-membered rings in 3 and 4 result from dimeric Mn(II) units bridged by H2tbip or H2mip ligands, which are connected by the flexible dpa into 2D open layers. Complex 5 contains rare isophthalato-bridged trimanganese clusters as building units, which are further linked by mip anions to form a one-dimensional ladder-like chain with less common unidentate coordinated bpp decorated as pendants. The thermal stabilities and X-ray powder diffraction studies indicate that the microporous framework of 2 can keep stable even after the loss of guest water molecules. In addition, dominant antiferromagnetic coupling was observed in compounds 1–3 and 5.

Synthesis, structures and properties of Mn(II) coordination frameworks based on R-isophthalate (R = –CH3 or –C(CH3)3) and various dipyridyl-type co-ligands

Six new Cd(II) coordination polymers, namely, {[Cd2(CH3O-ip)2(1,3-btp)2(H2O)2]·7H2O}n (1), {[Cd(CH3O-ip)(1,3-bip)]·H2O}n (2), {[Cd(CH3O-ip)(1,4-btb)0.5(H2O)]·2H2O}n (3), {[Cd(CH3-ip)(1,3-btp)(H2O)]·H2O}n (4), {[Cd(CH3-ip)(1,6-bth)(H2O)]·H2O}n (5), {[Cd(CH3-ip)(1,4-btb)0.5(H2O)]·H2O}n (6) (CH3O–H2ip = 5-methoxyisophthalic acid, CH3–H2ip = 5-methylisophthalic acid, 1,3-btp = 1,3-bis(1,2,4-triazol-1-yl)propane, 1,3-bip = 1,3-bis(imidazol)propane, 1,4-btb = 1,4-bis(1,2,4-triazol-1-yl)butane, 1,6-bth = 1,6-bis(1,2,4-triazol-1-yl)hexane), were obtained under hydrothermal conditions. Complex 1 exhibits a 3-D supramolecular network constructed from a 2-D helical layer. Complex 2 has a (3,5)-connected 2-D layer with a (42·6)(42·67·8) topology. Complexes 3 and 6 feature a 3-D supramolecular structure constructed from (3,4)-connected 2-D layers with a (42·6)(42·63·8) topology. Complex 4 shows the interdigitation of 2-D nets between two puckered (4,4) sheets. Complex 5 possesses an extended 3-D supramolecular architecture based on 2-D (4,4) layers. Moreover, the photoluminescent properties and UV-vis absorption spectra of the six complexes were investigated.

Construction of Cd(II) coordination polymers based on R-isophthalate (R = –CH3 or –OCH3) and flexible N-donor co-ligands: Syntheses, structures and photoluminescence

The invention relates to a 5-bromoisophthalic acid zinc complex and a preparation method thereof. The chemical formula of the complex is shown in the specification, wherein L is a 5-bromoisophthalic acid anionic ligand, and dpds is 4, 4'-bis(4-pyridyl) disulfide. The preparation method comprises the following steps: dissolving 5-bromoisophthalic acid, alkali, dpds and a metal zinc salt in water under hydrothermal conditions, sealing in a reaction kettle, heating to a certain temperature at the rate of 10 DEG C/hour, maintaining the temperature for 3 days, and then naturally cooling to room temperature to get a product disclosed by the invention. The complex has the advantages of good stability, simplicity in synthesis, convenience in operation, high yield, good reproducibility and the like, and an obtained crystalline material is expected to get further research and development applications in the field of fluorescent materials.

5-bromoisophthalic acid zinc complex and preparation method thereof

A novel zinc complex formulated as [Zn(Bript)(bpa)(H2O)]n (1) (H2Bript = 4-bromoisophthalic acid, bpa = 1,2-bi(4-pyridyl)ethane) has been synthesized through hydrothermal reaction. It was structurally characterized by elemental analysis and x-ray single-crystal diffraction. The x-ray crystal structure shows that the complex belongs to monoclinic systems, P21/n space group, and a = 10.997(6) A, b = 14.578(8) A, c = 12.963(7) A, β = 105.993(6)°. The adjacent Zn atoms are bridged by Bript to form a one-dimensional (1D) chain. Such 1D chains are further connected by hydrogen bonding to generate a three-dimensional (3D) supramolecular network. Fluorescence measurements show that 1 has medium fluorescent emissions at 404 nm and 468 nm upon excitation at 288 nm.

Jian-Ge Wang

Papers

Synthesis, structures and properties of Mn(II) coordination frameworks based on R-isophthalate (R = –CH3 or –C(CH3)3) and various dipyridyl-type co-ligands

Construction of Cd(II) coordination polymers based on R-isophthalate (R = –CH3 or –OCH3) and flexible N-donor co-ligands: Syntheses, structures and photoluminescence

5-bromoisophthalic acid zinc complex and preparation method thereof

A Zinc Complex Based on 4-Bromoisophthalic Acid and 1,2-Bi(4-pyridyl)ethane: Hydrothermal Synthesis, Crystal Structure, and Fluorescent Properties