Metal−Organic Framework Based on [Zn<sub>4</sub>O(COO)<sub>6</sub>] Clusters: Rare 3D Kagomé Topology and Luminescence

Qi, Yue; Sun, Qian; Cheng, Ai-Ling; Gao, En‐Qing

doi:10.1021/cg901312t

Cited by 50 publications

(16 citation statements)

References 26 publications

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“…Polymetric metal-organic complexes have attracted much attention in recent decades because of their fascinating topologies (Eddaoudi et al, 2002;Chakrabary et al, 2011) and enormous potential for many practical applications, such as gas storage (Li & Yang, 2007;Kim et al, 2013), heterogeneous catalysis (Huang et al, 2013), drug delivery (Horcajada et al, 2008), ion exchange (Genna et al, 2013), luminescence and chemical sensing (Yang et al, 2013). It is well known that fluorene is an excellent chromophore and has been widely studied in the field of organic luminescence (Yue et al, 2010;Peterson et al, 2011). Cuprous compounds have also been investigated as potential optical materials (Fang et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

The coordination chemistry of two symmetric fluorene-based organic ligands with cuprous chloride

Liu

Zhao

et al. 2013

Acta Crystallogr C

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Two novel symmetric fluorene-based ligands, namely, 2,7-bis(1H-imidazol-1-yl)-9,9-dimethyl-9H-fluorene [L1 or (I), C21H18N4] and 2,7-bis(1H-imidazol-1-yl)-9,9-dipropyl-9H-fluorene (L2), have been used to construct the coordination polymers catena-poly[[dichloridodicopper(I)(Cu-Cu)]-μ-2,7-bis(1H-imidazol-1-yl)-9,9-dimethyl-9H-fluorene], [Cu2Cl2(C21H18N4)]n, (II), and catena-poly[[tetra-μ2-chlorido-tetracopper(I)]-bis[μ-2,7-bis(1H-imidazol-1-yl)-9,9-dipropyl-9H-fluorene]], [Cu4Cl4(C25H26N4)2]n, (III). There are three types of C-H···N hydrogen bonds in (I), resulting a two-dimensional network in the ab plane, including a chiral helical chain along the b axis. Compounds (II) and (III) are related one-dimensional polymers. In both, Cu(I) atoms connect the symmetric ligands (L1 or L2) into a one-dimensional chain. In (II), the {[Cu(I)Cl2](-)} unit, acting as a co-anion, adheres to the one-dimensional chain through a weak Cu···Cu interaction. However, in (III), the {[Cu(I)2Cl4](2-)} unit links two different chains into a one-dimensional rope-ladder-type chain. In addition, there are C-H···Cl hydrogen bonds and π-π interactions in the extended structures of (II) and (III), the difference is that the chains in (II) are linked into a two-dimensional network while the chains in (III) are stacked into a three-dimensional framework.

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Section: Introductionmentioning

confidence: 99%

The coordination chemistry of two symmetric fluorene-based organic ligands with cuprous chloride

Liu

Zhao

et al. 2013

Acta Crystallogr C

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“…Notably, the group of Gao reported in 2010 the synthesis of a rare Kagométopology with a five-coordinate trigonal-bipyramidal geometry for one of the Zn 2+ ions and an octahedral geometry for another after binding of two DMSO molecules. 35 We also investigated the formation of network structures using the metalloligand 4 having less sterically demanding phenolatodioximato ligands (bromo instead of tert-butyl). The solvothermal treatment of 4 with Zn(NO 3 ) 2 (H 2 O) 6 in a DMF/ DEF mixture at 120 °C resulted in the formation of orange cubic single crystals of the MOF 20 (Scheme 6).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Carboxylic Acid Functionalized Clathrochelate Complexes: Large, Robust, and Easy-to-Access Metalloligands

Marmier¹,

Wise²,

Holstein

et al. 2016

Inorg. Chem.

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Polycarboxylate ligands are among the most important building blocks for the synthesis of metal-organic frameworks (MOFs). The ability to access these ligands in an efficient way is of key importance for future applications of MOFs. Here, we demonstrate that mono- and dinuclear clathrochelate complexes are versatile scaffolds for the preparation of polytopic carboxylate ligands. The largely inert clathrochelate complexes have a trigonal-bipyramidal shape. The synthesis of functionalized clathrochelates with two, three, four, or five carboxylic acid groups in the ligand periphery can be achieved in a few steps from simple starting materials. Apart from being easily accessible, the metalloligands display interesting characteristics for applications in metallasupramolecular chemistry and materials science: they are rigid, large (up to 2.2 nm), and robust and they can show additional functions (e.g., fluorescence or extra charge) depending on the metal ion that is present in the clathrochelate core. The utility of these new metalloligands in MOF chemistry is demonstrated by the synthesis of zinc- and zirconium-based coordination polymers. The combination of Zn(NO3)2 with clathrochelates having two or three carboxylic acid groups gives MOFs in which the clathrochelate ligands are connected by Zn4O clusters or zinc paddlewheel links. The structures of the resulting two- and three-dimensional networks could be established by single-crystal X-ray crystallography. The reaction of carboxylic acid functionalized clathrochelates with ZrCl4 gives amorphous powders that display permanent porosity after solvent removal.

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“…The ligand exhibits high-energy bands at 220 and 327 nm due to π-π* transitions. The less intense absorptions at 220 and 327 nm are tentatively ascribed to the admixture of metal-to-ligand transitions [17].…”

Section: Uv/vis Absorption and Photoluminescence Spectramentioning

confidence: 92%

Synthesis, Crystal Structure and Magnetic Properties of a Mn(II) Fluorenedicarboxylate Complex

Zhao

Zha

et al. 2013

Zeitschrift Für Naturforschung B

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A new Mn(II) metal-organic framework, [Mn(DFDC)(phen)] n (1) (where H 2 DFDC = 9,9-diethylfluorene-2,7-dicarboxylic acid, phen = 1,10-phenanthroline), was solvothermally synthesized and characterized by single-crystal and powder X-ray diffraction (PXRD), elemental and thermal analysis, IR, UV/Vis spectroscopy, fluorescence and magnetic measurements. Single-crystal X-ray analysis reveals that 1 exhibits a three-dimensional coordination polymer structure. The compound crystallizes in the orthorhombic space group Pnna with a = 9.1215(9), b = 26.436(3), c = 10.2428(10)Å, V = 2469.9(4)Å 3 , Z = 4, final wR2 = 0.1323 for 2825 reflections. The Mn(II) ion is coordinated by four oxygen atoms from four different H 2 DFDC ligands and two nitrogen atoms from one phen ligand in an octahedral coordination geometry. The compound shows ferromagnetic coupling behavior and has high thermal stability up to 420 • C.

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Metal−Organic Framework Based on [Zn₄O(COO)₆] Clusters: Rare 3D Kagomé Topology and Luminescence

Cited by 50 publications

References 26 publications

The coordination chemistry of two symmetric fluorene-based organic ligands with cuprous chloride

The coordination chemistry of two symmetric fluorene-based organic ligands with cuprous chloride

Carboxylic Acid Functionalized Clathrochelate Complexes: Large, Robust, and Easy-to-Access Metalloligands

Synthesis, Crystal Structure and Magnetic Properties of a Mn(II) Fluorenedicarboxylate Complex

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Metal−Organic Framework Based on [Zn4O(COO)6] Clusters: Rare 3D Kagomé Topology and Luminescence

Cited by 50 publications

References 26 publications

The coordination chemistry of two symmetric fluorene-based organic ligands with cuprous chloride

The coordination chemistry of two symmetric fluorene-based organic ligands with cuprous chloride

Carboxylic Acid Functionalized Clathrochelate Complexes: Large, Robust, and Easy-to-Access Metalloligands

Synthesis, Crystal Structure and Magnetic Properties of a Mn(II) Fluorenedicarboxylate Complex

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Metal−Organic Framework Based on [Zn₄O(COO)₆] Clusters: Rare 3D Kagomé Topology and Luminescence