Entanglement is one of the most important features of coordination polymer frameworks and has attracted considerable attention due to its aesthetic and topological interest. Among entangled systems, interpenetrating frameworks represent an intriguing subset; however, there are few examples of materials containing very high levels of interpenetration. In this work a coordination polymer with 10(3)-srs topology, constructed from a star-like tridentate ligand, tri(4-imidazolylphenyl)amine, and Ag(I) ions, has been hydrothermally synthesized. It contains a record 54 interpenetrating networks.

A novel coordination polymer [[Cu(L(1))(L(2))(H(2)O)].5H(2)O](n) (1), where L(1) =1,1'-(1,4-butanediyl)bis(imidazole) and L(2) = m-phthalate anion, has been obtained by using an unusual crystallization process. It crystallizes in the orthorhombic space group Pna2(1), which belongs to the crystal class mm2, with a = 9.0521(18), b = 15.401(3), and c = 17.141(3) A, alpha = beta = gamma = 90 degrees, V = 2389.7(8) A(3), and Z = 4. The complex 1 composing a porous supramolecular architecture displays unprecedented four-connected topology of an 8(6) net in coordination polymer chemistry. Thermal gravimetric analysis (TGA) and X-ray powder diffraction (XRPD) patterns for 1 are discussed in detail.

Six new coordination polymers, namely [Zn1.5(BTC)(L1)(H2O)2].1.5H2O (1), [Zn3(BTC)2(L2)3] (2), [Zn3(BTC)2(L3)1.5(H2O)].H2O (3), [Co6(BTC)4(L1)6(H2O)3].9H2O (4), [Co1.5(BTC)(L2)1.5].0.25H2O (5), and [Co4(BTC)2(L3)2(OH)2(H2O)].4.5H2O (6), where L1 = 1,2-bis(imidazol-1-ylmethyl)benzene, L2 = 1,3-bis(imidazol-1-ylmethyl)benzene, L3 = 1,1'-(1,4-butanediyl)bis(imidazole), and BTC = 1,3,5-benzenetricarboxylate anion, were synthesized under hydrothermal conditions. In 1-6, each of L1-L3 serves as a bidentate bridging ligand. In 1, BTC anions act as tridentate ligands, and compound 1 shows a 2D polymeric structure which consists of 2-fold interpenetrating (6, 3) networks. In compound 2, BTC anions coordinate to zinc cations as tridentate ligands to form a net with (64.82)2(86)(62.8)2 topology. In compound 3, BTC anions act as tetradentate ligands and coordinate to zinc cations to form a net with (4.62.83)2(8.102)(4.6.83.10)2 topology. In compound 5, each BTC anion coordinates to three Co cations, and the framework of 5 can be simplified as (64.82)2(62.82.102)(63)2 topology. For 4 and 6, the 2D cobalt-BTC layers are linked by bis(imidazole) ligands to form 3D frameworks. In 6, the Co centers are connected by micro3-OH and carboxylate O atoms to form two kinds of cobalt-oxygen clusters. Thermogravimetric analyses (TGA) for these compounds are discussed. The luminescent properties for 1-3 and magnetic properties for 4-6 are also discussed in detail.

We describe here two unusual polyrotaxane-like metal-organic frameworks of [Co2(1,3-bix)2(bpea)2] and [Cd4(1,4-bix)4(bpea)4] x 4H2O , where both species contain loops and rods that are interlaced in a highly rare "parallel" fashion in , but, uniquely, in an "inclined" fashion in .

An investigation into the dependence of coordination polymer architectures on organic-acid ligands is reported on the basis of the reaction of Pb(NO3)2 and eight structurally related organic-acid ligands in the presence or absence of N-donor chelating ligands. Eight novel lead(II)-organic architectures, [Pb(adip)(dpdp)]2 1, [Pb(glu)(dpdp)] 2, [Pb(suc)(dpdp)] 3, [Pb(fum)(dpdp)] . H2O 4, [Pb2(oba)(dpdp)2] . 2(dpdp).2(NO3).2H2O 5, [Pb2(1,4-bdc)2(dpdp)2] . H2O 6, [Pb(dpdc)(dpdp)] 7, and [Pb(1,3-bdc)(dpdp)] . H2O 8, where dpdp = dipyrido[3,2-a:2',3'-c]-phenazine, H2adip = adipic acid, H2glu = glutaric acid, H2suc = succinic acid, H2fum = fumaric acid, H2oba = 4,4'-oxybis(benzoic acid), 1,4-H2bdc = benzene-1,4-dicarboxylic acid, H2dpdc = 2,2'-diphenyldicarboxylic acid, and 1,3-H2bdc = benzene-1,3-dicarboxylic acid, were successfully synthesized under hydrothermal conditions through varying the organic-acid linkers and structurally characterized by X-ray crystallography. Compounds 1-8 crystallize in the presence of organic-acid linkers as well as secondary N-donor chelating ligands. Diverse structures were observed for these complexes. 1 and 5 have dinuclear structures, which are further stacked via strong pi-pi interactions to form 2D layers. 2-3 and 6-8 feature chain structures, which are connected by strong pi-pi interactions to result in 2D and 3D supramolecular architectures. Compound 4 contains 2D layers, which are further extended to a 3D structure by pi-pi interactions. A systematic structural comparison of these 8 complexes indicates that the organic-acid structures have essential roles in the framework formation of the Pb(II) complexes.

Four novel highly connected metal−organic frameworks (MOFs) based on d 10 metals and triangular ligands, namely, [Ag 7 (4,4′-tmbpt4-triazole, and 3,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3pyridyl)-5-(4-pyridyl)-1,2,4-triazole) have been synthesized under hydrothermal conditions. Compound 1 features a three-dimensional (3D) (3,12)-connected net based on heptanuclear [Ag 7 (COO) 7 ] units. Compound 2 displays a 3D (3,4,10)-connected net constructed by tetranuclear [NaCd 3 (μ 3 -OH)(COO) 5 ] + units. Compound 3 exhibits a 3D (3,4,8)-connected net based on binuclear [Cd 2 (COO) 2 ] units. Compound 4 is a 3D binodal (3,9)-connected framework constructed by trinuclear [Cd 3 (COO) 4 ] units. The diverse structures of compounds 1−4 indicate that the central metals and the N-donor ligands have significant effects on the final structures. The photoluminescent properties of compounds 1−4 have been studied in detail. Remarkably, compounds 1, 2, and 4 exhibit photocatalytic activities for degradation of dye under UV light irradiation and show good stabilities toward UV-light photocatalysis.

Nine new coordination polymers, namely, [Mn(2)(L)(H(2)O)(4)].H(2)O (1), [Cd(L)(0.5)(H(2)O)] (2), [Zn(5)(L)(2)(mu(3)-O)(2)(H(2)O)(4)].2H(2)O (3), [Zn(4)(L)(2)(mu(3)-O)(2)][Zn(H(2)O)(5)].2H(2)O (4), [Zn(2)(L)(biim-4)(0.5)(H(2)O)(3)].H(2)O (5), [Cd(2)(L)(bpy)(H(2)O)].2H(2)O.0.5(CH(3)CH(2)OH) (6), [Cu(2)(H(2)L)(2)(bpy)(2)] (7), [Cu(2)(L)(bpy)(H(2)O)] (8), and [Cu(2)(L)(bpy)(1.5)(H(2)O)(2.5)] (9), where H(4)L = 1,2,3,4-benzenetetracarboxylic acid, biim-4 = 1,1'-(1,4-butanediyl)bis(imidazole), and bpy = 4,4'-bipyridine, have been synthesized under hydrothermal conditions. Compound 1 displays a rare trinodal (3,4,7)-connected (4(2).6)(4(5).6)(4(7).6(8).8(6)) topology. 2 possesses an alpha-Po net. 3 is a novel 3D framework based on pentanuclear Zn(II) clusters. By adjustment of the pH values of the reaction mixture of 3 with a Na(2)CO(3) solution, a structurally different compound, 4, was obtained, which exhibits a 3D porous framework with the [Zn(H(2)O)(6)](2+) cations located in the channels. 5 is an unusual example of a trinodal (3,5)-connected network with a Schlafli symbol of (4(2).6)(6(2).8)(4(2).6(2).8(5).10), whereas 6, containing tetranuclear Cd(II) clusters, shows a rare (4,6)-connected (4(4).6(2))(2)(4(4).6(10).8) topology. 7 exhibits a unique polythreading network, while 8 displays a scarce trinodal (3,4,5)-connected self-penetrating network. In comparison with 8, the chiral compound 9 possesses an unprecedented tetranodal (2,4)-connected (7)(7(5).11)(6(2).7(3).8)(2)(6.7(4).10)(2) topology. The effects of the carboxylate ligands, the pH values, the reaction temperatures, the central metals, and the neutral ligands were elucidated. The IR spectra, thermogravimetric analysis, and luminescent properties for the compounds were also investigated.

By varying the fluorescent tags of resorcin[4]arene-based tetracarboxylic acids from phenyl to naphthyl, two highly luminescent metal-organic frameworks (MOFs), namely, [Zn2(TPC4A)(DMF)(H2O)4]·3H2O (1) and [(CH3)2NH2]2[Zn(TNC4A)]·4H2O (2), were successfully achieved (TPC4A = 2,8,14,20-tetra-phenyl-6,12,18,24-tetra-methoxy-4,10,16,22-tetra-carboxy-methoxy-resorcin[4]arene and TNC4A = 2,8,14,20-tetra-1-naphthal-6,12,18,24-tetra- methoxy-4,10,16,22-tetra-carboxy-methoxy-resorcin[4]arene). Compound 1 features a unique 2D network, while 2 exhibits a fascinating 3D framework. The highly selective detection of small organic molecules as well as Fe(2+) and Fe(3+) was performed for 1 and 2 as fluorescent sensors. Remarkably, luminescent 1 and 2 were used as sensory materials for the sensing of various amine vapors with high selectivity and rapid response. Most strikingly, clear fluorescence "on-off" switch-functions toward small organic molecules as well as amine vapors were also explored for luminescent 1 and 2.