An unprecedented (4, 8)-connected self-penetrating Cu(I)-MOF constructed from the rare [Cu4I2]2 + cationic cluster and in situ generated tetrazole ligand

The in situ hydrothermal reaction of CuI, NaN₃ and 4-(1H-imidazol-1-yl)benzonitrile leads to a new three-dimensional pillared-layer Cu(I)-MOF, [Cu₂(μ₃-I)(μ₅-IPT)]_n (1) (HIPT = 5-[4-(imidazol-1-yl)phenyl]tetrazolate). Interestingly, the structure of 1 exhibits an unprecedented binodal (4, 8)-connected three-dimensional self-penetrating framework first constructed from [Cu₄I₂]^2 + cationic clusters as 8-connected nodes and in situ generated IPT ligands as 4-connected nodes. Moreover, 1 is strongly luminescent with green emission (λ_em = 545 nm) in the solid-state.     

Self-assembly of a novel 3D copper(I)-tetrazolate supramolecular framework via interpenetration of porous 2D double-layer motifs

The self-assembly of CuCN and 1H-TAZ ligand under hydrothermal conditions generated a novel three-dimensional hybrid supramolecular framework, namely, [Cu₆(TAZ)₄(CN)₂]_n (1) (TAZ = tetrazole). Single-crystal X-ray diffraction show that [Cu₂(TAZ)₂] binuclear subunits are linked by μ₂- and μ₃-CN groups to give a 2D double-wave-shaped network, which possesses 1D channels with four open-windows. The 2D bilayers interpenetrated each other to form the 3D supramolecular framework of 1.     

Syntheses,structures and luminescence of three copper(I) cyanide coordination polymers incorporating flexible N-donor ligands

Three copper(I) cyanide coordination polymers, namely [Cu₈(CN)₈(btmb)₂]_n (1), [Cu(CN)(btmb)_0.5]_n (2) and [Cu₂(CN)₂(dpa)]_n (3) (btmb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, dpa = di(4-pyridyl)amine), were synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectra, PXRD and thermogravimetric analyses. Single-crystal X-ray diffraction analyses reveal that complex 1 is an interesting 2D double-layered network constructing from eight distinct Cu(I) centers, eight μ₂-cyanides and two tetradentate cis-btmb ligands. Complex 2 is a ladder-like coordination polymer assembled by CuCN linear chain and bidentate trans-btmb linker. Complex 3 has a 2D wave-like network constructing from CuCN zigzag chain and V-shape dpa spacer. These coordination polymers are thermally stable up to 270–300 °C. They emit blue luminescence originating from ligand-centered emission.     

A new Cu-based metal-organic framework built upon infinite 1D rod-shaped secondary building units

A new Cu(II) metal-organic framework {[Cu_1.5(1,3-bdc)(dtb)(OH)(H₂O)](H₂O)}_n (1) (1,3-H₂bdc = 1,3-benzenedicarboxylic acid, dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene), has been synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, and IR spectra. Compound 1 features a 3-D open framework constructed by infinite 1D rod-shaped [Cu₃(OH)₂]_n chains as secondary building units. The magnetic property of the complex has also been investigated.     

Hydrothermal synthesis,crystal structure and optical properties of a 2-D heterometallic iodoplumbate

A novel two-dimensional heterometallic iodoplumbate, [Pb₃I₁₀Cu₄(phen)₂]_n (phen = 1,10-phenanthroline) constructed from [Pb₃I₁₀]^4? iodoplumbate chains and [Cu₂I₄(phen)]^2? entities has been hydrothermally synthesized and structurally characterized. The solid compound exhibits an intriguing semiconducting property with E_g = 2.62 eV. The thermochromic behavior of the compound has been also studied.     

A chiral 3D polymer with right- and left-helices based on 2,2′-biimidazole: Synthesis,crystal structure and fluorescent property

A novel three-dimensional (3D) polymer [Cd₂(Hbiim)₄]_n (H₂biim = 2,2′-biimidazole) 1 was obtained through hydrothermal reaction and characterized by single crystal X-ray diffraction, and the fluorescent property was also determined. Compound 1 crystallizes in a monoclinic chiral space group P2₁ and contains two types of helical chains. Hbiim⁻ partially deprotonated of H₂biim exhibits two different coordination modes, which contributes greatly to the formation of the 3D chiral framework. Compound 1 exhibits blue fluorescence at 488 nm in the solid-state upon excitation at 430 nm.     

Structures and photoluminescence of coordination polymers assembled from bifunctional ligand containing both tetrazole and imidazole groups

Three new coordination polymers, namely, {[Cu₂(IPT)(SO₄)(OH)(H₂O)]·H₂O}_n (HIPT = 5-(4-(1H-imidazol-1-yl)phenyl)- 1H-tetrazolate, 1), {[Cd₂(IPT)(NPA)(OH)]·H₂O}_n (H₂NPA = 5-nitroisophthalic acid, 2), and {[Zn₂(IPT)(IDC)(H₂O)]·3H₂O}_n (H₃IDC = 1H-imidazole-4,5-dicarboxylic acid, 3), were assembled from a bifunctional organic ligand containing both tetrazole and imidazole groups with/without the aid of carboxylate coligands. Compound 1 possesses 2D structure built by 1D [Cu₂(IPT)(SO₄)(OH)]_n secondary building blocks and IPT⁻ linkers. The 2D networks are linked into 3D supramolecular framework via water chains in helical conformation. Compound 2 displays 3D pillar-layer framework with 2D layers based on tetranuclear Cd(II) SBUs and NPA^2 − pillars. Compound 3 exhibits a 3D framework constructed from the interconnection of 1D [Zn-IDC]_n chains and binuclear Zn₂(IPT)₂ rings. The thermal stabilities of porous compound 3 and luminescent properties of compounds 2 and 3 have also been studied in detail. They exhibit intense solid-state fluorescent emissions at room temperature.     

A red luminescent organic–inorganic hybrid network with double-stranded zigzag [Cu4I4]n chains

A novel red luminescent coordination polymer, [Cu₂I₂(bmt)]_n·nDMF (1), was synthesized from the solution reaction of CuI and heterocyclic thione ligand, benz-1,3-imidazole-2-thione (bmt). Single-crystal analysis shows that its unusual organic–inorganic hybrid framework built-up from the distorted double-stranded zigzag [Cu₄I₄]_n chains with organic bmt ligands. Emission properties of 1 in solid state at room temperature and 10 K were investigated.     

Self-assembly of a two-dimensional cluster coordination polymer {[W2S8Cu8I4(bpe)2(py)2] · H2O}n: Crystal structure and luminescent properties

A cluster coordination polymer {[W₂S₈Cu₈I₄(bpe)₂(py)₂] · H₂O}_n1 [bpe = 1,2-bis(4-pyridyl)ethane, py = pyridine] has been synthesized and characterized by single-crystal X-ray diffraction and luminescent spectrum. The crystal data for 1: crystal system, tetragonal, space group P4₂, a = 12.7023(13), b = 12.7023(13), c = 13.3621(19), V = 2156.0(4), Z = 1, D_c = 2.089, Flack parameter = 0.093(16), R₁ = 0.0548, and wR₂ = 0.1533. The structure analysis reveals that 1 is the first two-dimensional noninterpenetrating cluster coordination polymer with chiral space group based on the heterothiometallic pentanuclear [WS₄Cu₄] as secondary building units (SBUs). Coordination polymer 1 exhibits intense luminescent spectrum at 615 nm in the solid state with the excitation peak at 344 nm.     

Synthesis,crystal structure and magnetic properties of a new cyanide-bridged mixed-valence copper(I)/copper(II) clathrate

A unique cyanide-bridge mixed-valence Cu^I/Cu^II clathrate of formula [Cu^I₂(CN)₃][{Cu^II(tren)}₂(μ-CN)](CF₃SO₃)₂ [tren = tris(2-aminoethyl)amine] containing cyanide-bridged [{Cu^II(tren)}₂(μ-CN)]^3 + binuclear cations stacked between anionic honeycomb layered copper(I) cyanide networks, was synthesized and structurally characterized by single crystal X-ray diffraction. Variable-temperature magnetic susceptibility studies showed that the cyanide bridge mediates a strong antiferromagnetic interaction between the copper(II) centers (J = − 160 cm^− 1, the spin Hamiltonian being defined as H = −J S_A⋅S_B).     

Hydrothermal syntheses and crystal structures of PbII coordination polymers based on a N,O-donor ligand

In this article, four new lead(II) coordination polymers based on a N,O-donor ligand 2′-(1 H-1,3,7,8-tetraaza-cyclopenta[l]phenanthren-2-yl)biphenyl-2-carboxylic acid (HL) have been hydrothermally synthesized, namely, [PbL₂]·2H₂O (1), [PbL₂]·2H₂O·CH₃CH₂OH (2), [Pb₅L₂(m-BDC)₄]·3H₂O (3) and [Pb₂L₂(p-BDC)] (4), where m-BDC = 1,3-benzenedicarboxylate and p-BDC = 1,4-benzenedicarboxylate. Compound 1 shows a 2D bilayer structure, which is further extended into a 3D supramolecular structure through π–π stacking interactions. Compound 2 shows a 3D supramolecular structure based on a zero-dimensional molecule by π–π stacking interactions of neighboring molecules. Compound 3 shows a 2D layer structure. Compound 4 displays a 1D chain-like structure, which is then stacked by π–π interactions to result in a 2D supramolecular structure. Solid-state luminescent spectra of four lead(II) complexes indicate intense fluorescent emissions.     

Syntheses,topological analyses and magnetic properties of two 3D supramolecular nickel-organic frameworks constructed from 1,3,5-benzenetricarboxylate and flexible imidazole-based ligands

Two supramolecular nickel-organic frameworks, [Ni(HBTC)(bix)]_n (1) and [Ni₃(BTC)₂(mbix)₃(H₂O)₄]_n · 6nH₂O (2) (bix = 1,4-bis(imidazole-l-yl-methyl)benzene, mbix = 1,3-bis(imidazole-l-yl-methyl)benzene, and H₃BTC = 1,3,5-benzenetricarboxylate), have been hydrothermally prepared by the assembly of H₃BTC, Ni²⁺ with bix or mbix. Compound 1 shows a 2D layer structure, whose 3D supramolecular structure exhibits a fsc topology when hydrogen-bonging interactions between the adjacent layers are taken into account. Compound 2 manifests an unprecedented 2D (3, 4)-connected topological net. The 3D supramolecular framework of 2 is formed through π?π stacking interactions between the adjacent layers. The magnetic studies show that 1 features overall ferromagnetic property whilst 2 presents strong zero-field splitting (ZFS) when treated as a mononuclear model. Furthermore, the IR and TGA properties of 1 and 2 were also studied.     

Self-assembly of novel supramolecular silver(I) compound based on mixed ligands bipy/TST3−, H3TST = 2,4,6-tris (4-sulfophenylamino)-1,3,5-triazine

The novel supramolecular silver(I) compound with formula [Ag₆(TST)₂(bipy)₆(H₂O)₂]_n · 3nH₂O (1) based on assembly of Ag(I) and mixed ligand bipy/TST³⁻, bipy = 2,2′-bipyridine, H₃TST = 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, has been prepared by hydrothermal method. In the solid-state structure of 1, two-dimensional layered polymeric structures extended with subunits [Ag₆(TST)₂(bipy)₆(H₂O)₂] interact each other in the form of π–π attractions between bipy, forming a three-dimensional supramolecular architecture. Compound 1 represents a Ag-containing polymeric compound possessing room-temperature luminescence.     

Construction of two mixed-ligand coordination polymers presenting unusual polyrotaxane-like entanglements

Two novel polyrotaxane-like coordination polymers, [Ni₄(L)₄(H₂O)₃(bpp)₄]·3H₂O (1) and [Cd₄(L)₄(bpp)₃]·3H₂O (2) (H₂L = Me₂Si(p-C₆H₄COOH)₂, bpp = 1,3-bis(4-pyridyl)propane), have been synthesized and structurally characterized. Compound 1 features a 2D → 3D polyrotaxane array by the interlock of bilayer networks. Compound 2 exhibits an unusual 3D polyrotaxane-like self-threading framework. In addition, compound 2 shows an emission at 485 nm when it was excitated at 400 nm.     

Syntheses,structures and luminescent properties of two new two-fold interpenetrating 2D coordination polymers based on 4′-(4-carboxyphenyl)-4,2′:6′,4″-terpyridine

Two new coordination polymers, [Zn₂(cptpy)₂Cl₂]_n·0.5nH₂O (1) and [Cd₂(cptpy)₄]_n·3.5nH₂O (2) (Hcptpy = 4′-(4-carboxyphenyl)-4,2′:6′,4″-terpyridine), were synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 shows a new two-fold interpenetrating 3-connected 2D framework with the hcb topological net and the Schläfli symbol of 6³. Compound 2 displays a two-fold interpenetrating (4,4)-connected 2D framework with the sql topological net and the Schläfli symbol of {4⁴ · 6²}. Interestingly, compounds 1 and 2 were obtained in the similar reaction conditions. The structural diversity of compounds 1 and 2 may illustrate the marked effect of the metal ion of the reaction solution. Additionally, photoluminescence properties of compounds 1–2 have been investigated.     

Cyanide-bridged mixed-valence copper(II/I) coordination polymers: Unique 7-connected sev-type 3D network versus anionic 2D host network encapsulated with cationic complex

Reactions of CuCl₂, K₂[Ni(CN)₄]/K₃[Co(CN)₆], and 5-amino-1H-tetrazole led to cyanide-bridged mixed-valence Cu(II/I) complexes, [Cu(H₂O)₃Cu₃(CN)₅] (1) and [Cu(H₂O)₄][Cu₄(CN)₆] (2).The uncommon semi-closed {Cu₂(CN)₃} dimmers in 1 are bridged by μ₃-C,C,N cyanide ligands to afford rare 1D centipedal-like chain motifs, which are further bridged by μ₂-C,N and metalloligand “CN–Cu(4)–CN” to finish sophisticated zeolite-like 3-D structure. Topologically, 1 is the first example of uninodal 7-connected sev-like cyanide-bridged network. Compound 2 consists of two-dimensional honeycomb-related anionic layers [Cu₄(CN)₆]^2 −, within which the [Cu(H₂O)₄]^2 + cations are intercalated into alternate interlamellar space. Compound 1 shows antiferromagnetic couple arising from pure ground-state configuration of Cu(II) mediated by diamagnetic bridges –CN–Cu^I–CN −. The inclusion compound 2 shows blue photoluminescence originated from Cu(I) center to the unoccupied π* orbital of the cyanide ligand (MLCT) charge transfer.     

Novel silver(I) compounds assembled from hybrid ligands based on linear or T-shaped coordination environment

Two novel 1D compounds {[Ag₃(Hbptc)(bpa)₂]·H₂O}_n (1) and [Ag₂(H₂bptc)(bpp)₂]_n (2) (H₄bptc = 3,3′,4,4′-benzophenonetetracarboxylic acid, bpa = 1,2-bis(4-pyridyl)ethane and bpp = 1,3-bis(4-pyridyl)propane) were synthesized and structurally characterized. The crystal structures of compounds exhibit two kinds of ladder-like chains based on linear or T-shaped coordination environment of Ag(I). Fluorescence spectra of compounds 1 and 2 indicate the unusual intensity of fluorescent emission upon photoexcitation which may be attributed to ligand-to-metal charge transfer and Ag–Ag interactions.     

A novel 3D POMOF based on dinuclear copper (II)-oxalate complexes and Keggin polyoxoanions with excellent photocatalytic activity

A novel coordination polymer, [Cu₂(btx)₂(C₂O₄)][H₂SiW₁₂O₄₀]·12H₂O (btx = 1,4-bis(triazol-1-ylmethyl)benzene)] (1) has been synthesized by hydrothermal reaction, and characterized by elemental analyses, IR spectroscopy, and single crystal X-ray diffraction. Compound 1 is composed of α-Keggin type [SiW₁₂O₄₀]^4 − polyoxoanions and dinuclear copper (II)-btx complexes. The dinuclear copper (II)-btx complex is a three-dimensional (3D) porous framework, in which the [SiW₁₂O₄₀]^4 − as 4-coordinating guests are encapsulated, forming a novel 3D POMOF with two kinds of open channels along both a and b axes. Additionally, compound 1 shows excellent photocatalytic properties for the degradation of methylene blue (MB) under both visible and ultraviolet (UV) light. The molecular design of 1 not only generates a new POMOF, but also opens a new avenue to produce photocatalytic materials.     

Two Keggin polyoxoanion-based hybrids composed of CuI/tbz segments: Syntheses,structures and electrochemical properties

Two Keggin polyoxoanion-based hybrid compounds composed of Cu^I/tbz segments [Cu^I₂(tbz)₂][Cu^I(tbz)₂(PMo^VI₁₀Mo₂^VO₄₀Cu^I₂)] (1) and [Cu^I₂(tbz)₃][Cu^I (tbz)₂](PW₁₂O₄₀) (2), have been hydrothermally synthesized. In compound 1, a 3D supramolecular framework with 2D channels is constructed from a novel cap-to-cap {Cu^I(tbz)₂(PMo^VI₁₀Mo₂^VO₄₀Cu^I₂)}^2 −_n chain via hydrogen bonding and π–π interactions, in which {Cu^I₂(tbz)₂}^2 + segments are incorporated. Compound 2 is composed of one discrete PW₁₂ polyoxoanion, one {Cu^I(tbz)₂}⁺ segment and one {Cu^I₂(tbz)₃}^2 + segment, displaying a 3D supramolecular structure through hydrogen bonding and π–π interactions. The results indicate that the polyoxoanions and configurations of tbz ligand play the key roles in the self-assembly processes. The electrochemical properties of compounds 1 and 2 have been investigated.     

Synthesis,characterization and crystal structure of one Cu(II) complex with flexible tetrapyridine and fatty acid ligand

One new title compound [Cu₂(TPOM)(adi)₂]_n · 4nH₂O (1) (TPOM = tetrakis(4-pyridyloxymethylene)methane, adi = adipic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction.