A New 10-Connected Coordination Network with Pentanuclear Zinc Clusters as Secondary Building Units

Eight new coordination polymers, [Zn(L)Cl] n (1), [Zn 2 (L) under hydrothermal conditions and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Complexes 1, 2, and 7 display a two-dimensional (2D) layer structure. Complex 3 presents a complicated 2D layer structure with paddle-wheel units, which exhibits an interesting (3,4,6)-connected 3-nodal new topological net with the point symbol of (3Complex 4 is a 2-nodal (3,5)-connected 2D bilayer structure with the gek1 topological net and the point symbol of (3•4•5)(3 2 •4•5•6 2 •7 4 ). Complex 5 shows a self-penetrating three-dimensional (3D) framework based on pentanuclear clusters, which features an intriguing (3,3,4,4,12)-connected 5-nodal new topological net with the point symbol of (4•6 2 ) 2 (4 2 •6 4 ) 4 (4 3 ) 2 (4 8 •6 34 •8 22 •10 2 ). Complex 6 features a 2-fold interpenetrating (3,4)-connected 3D framework with the ins topological net and the point symbol of (6 3 )(6 5 •8). Complex 8 is a new (4,4,5,6)-connected 3D network built up by a linear Cd 3 (COO) 6 trinuclear cluster with the point symbol of (4 2 •6 3 •8) 2 (4 3 •6 3 ) 2 (4 4 •6 4 •8 2 ) 2 (4 8 •6 6 •8). The diverse structures indicate that rational adjustment of the second ligand, the pH value, and counteranion are good methods to further design metal−organic compounds with new structures and properties. In addition, the thermal stabilities and photoluminescence properties of 1−8 were also studied.

Section: Resultssupporting

confidence: 85%

Synthesis, Crystal Structure, and Luminescence of Zn/Cd Coordination Polymers with a New Fuctionalized Terpyridyl Carboxylate Ligand

Xie

et al. 2014

“…Ligand-based luminescence properties are useful in the detection of metal ions . Because of enhanced stability of metal complexes compared to organic counterparts, coordination polymers are used as photoluminescent materials . Generally d 10 -metal coordination polymers exhibit photoluminescence properties .…”

Section: Resultsmentioning

confidence: 99%

Structures, Magnetic Properties, and Photoluminescence of Dicarboxylate Coordination Polymers of Mn, Co, Ni, Cu Having N-(4-Pyridylmethyl)-1,8-naphthalimide

Nath

Mondal

Powell

et al. 2014

Supramolecular interactions of N-(4-pyridylmethyl)-1,8-naphthalimide (L) and flexibility of intervening units of dicarboxylate ligands contribute to formation of different types of coordination polymers such as [MnL 2(Adp)(H2O)2] n ·2nH2O (1), [CoL 2(Fum)(H2O)2] n ·2nH2O (2), [CoL 2(Adp)(H2O)2] n ·2nH2O (3), [NiL(Fum)(H2O)3] n ·H2O (4), [CuL 2(Fum)] n ·nH2O (5), [CuL(Mal)] n (6), and [Cu3 L 6(Adp)3(H2O)3] n (7) (where Adp = adipate, Fum = fumarate, and Mal = malonate). These coordination polymers are structurally characterized. Coordination polymers 1 and 3 are isostructural having three-dimensional (3D) supramolecular layer-like structures. Coordination polymer 2 forms a two-dimensional (2D) supramolecular network through C–H···π and O···π interactions. Coordination polymer 4 forms H-bonded 3D chainlike supramolecular architecture. Coordination polymer 5 forms a 3D supramolecular sheet-like structure, whereas coordination polymer 6 and coordination polymer 7 forms a 2D lamellar structure through π···π and C–H···π interactions. Manganese coordination polymer 1 shows weak antiferromagnetic interactions between chains at low temperature and also exhibits single chain magnetic behavior. Coordination polymers 2 and 3 show saturation value of magnetic moment at 2 K and 7 T, which are lower than the spin-only Co(II) ion. Coordination polymer 4 show spin-only values for Ni(II) ion. The room-temperature χM T value for coordination polymer 5 is close to the spin-only value for two Cu(II) ions. With lowering of the temperature, the χM T value remains constant to 35 K, from where the value begins to decrease to a minimum at 2 K. For copper coordination polymer 6 value of χM T smoothly decreases with lowering of the temperature to attain a quasi plateau between 80 K and 35 K, and it further sharply increases at 2 K. Coordination polymer 7 shows spin-only Cu(II) ion. These coordination polymers in solid state show quenching of fluorescence emission of ligand L, as well as a shift of emission toward a shorter wavelength.

“…The 1,4-naphthalenedicarboxylic acid (H 2 NDC) ligand as an important aromatic carboxylic ligand has shown an excellent bridging role in constructing novel MOFs with interesting optical and magnetic properties as well as gas storage ability because of its various coordinating modes (Table ), high symmetry, and structural rigidity . However, up to now much more research on the coordination chemistry of the H 2 NDC ligand has been focused on transition-metal-based MOFs, and investigations on NDC-bridged Ln MOFs are very rare. For example, in 2004, Gao’s group reported two three-dimensional (3-D) MOFs, [Ln 7 (μ 3 -OH) 8 (NDC) 6 (OH) 0.5 (CH 3 COO) 0.5 (H 2 O) 7 ]·4H 2 O, constructed from unprecedented heptanuclear [Ln 7 (μ 3 -OH) 8 ] 13+ (Ln = Ho, Yb) cluster units .…”

Section: Introductionmentioning

confidence: 99%

Three-Dimensional Extended Frameworks Constructed from Dinuclear Lanthanide(III) 1,4-Naphthalenedicarboxylate Units with Bis(2,2′-biimidazole) Templates: Syntheses, Structures, and Magnetic and Luminescent Properties

Jian

Jin

et al. 2014

Eight unprecedented Ln-NDC coordination polymers with BBI as templates {[HBBI][Ln(NDC)2(H2O)]·H2O [Ln = La (1), Pr (2)], [HBBI]2[Sm(NDC)2(H2O)]2·1/2H2O (3), and [HBBI][Ln(NDC)2(H2O)] [Ln = Eu (4), Gd (5), Tb (6), Dy (7), Er (8)] [Ln = lanthanide, H2NDC = 1,4-naphthalenedicarboxylic acid, BBI = bis(2,2′-biimidazole)]} have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction. Complexes 1–8 crystallize in the monoclinic space group P21/c and display similar (8,8)-connected 3-D frameworks with different dinuclear Ln secondary building units due to the effect of Ln contraction and diverse coordination modes of NDC2– ligands. As the ionic radii of Ln ions decrease, the coordination numbers of Ln ions decrease from 10, to 9, to 8. The variable-temperature magnetic properties of 2–8 have been investigated. The strong fluorescent emissions of 4 demonstrate that ligand-to-EuIII energy transfer is efficient. In addition, thermogravimetric analyses and optical diffuse reflectance spectra of these compounds are also described.