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Dual stimuli-induced formation of a ?-hydroxido bridged [Zn₉L₅(?-OH)₆]¹²⁺ half-pipe.

ABSTRACT: Low-symmetry metal-organic architectures that feature unusual binding motifs are useful for exploring new modes of guest recognition. Such structures remain difficult to create using current rational design principles. One approach to constructing such architectures is to employ ligands with coordination vectors oriented to preclude the formation of simple, low nuclearity molecular assemblies upon complexation to metal ions. Here we report two new supramolecular assemblies generated from such a ligand: a simple metastable [Zn₃L₃]⁶⁺ assembly, which was observed to convert to a more complex [Zn₉L₅(?-OH)₆]¹²⁺ twisted half-pipe architecture. Two chemically distinct stimuli-an anionic template and a base-must be applied for the conversion to occur. Perchlorate, perrhenate, trifluoromethanesulfonate and 2-naphthalenesulfonate were found to act as competent templates for the [Zn₉L₅(?-OH)₆]¹²⁺ structure.

SUBMITTER: Wood CS

PROVIDER: S-EPMC5535065 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature

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Dual stimuli-induced formation of a μ-hydroxido bridged [Zn9L5(μ-OH)6]12+ half-pipe.

Wood Christopher S CS Ronson Tanya K TK McConnell Anna J AJ Roberts Derrick A DA Nitschke Jonathan R JR

Chemical science 20151117 3

Low-symmetry metal-organic architectures that feature unusual binding motifs are useful for exploring new modes of guest recognition. Such structures remain difficult to create using current rational design principles. One approach to constructing such architectures is to employ ligands with coordination vectors oriented to preclude the formation of simple, low nuclearity molecular assemblies upon complexation to metal ions. Here we report two new supramolecular assemblies generated from such a ...[more]

PMID: 28808538

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Project description:Fluoride ion (F-) is one of the most hazardous elements in potable water. Over intake of F- can give rise to dental fluorosis, kidney failure, or DNA damage. As a result, developing affordable, equipment-free and credible approaches for F- detection is an important task. In this work, a new three dimensional rare earth cluster-based metal-organic framework assembled from lanthanide Y(III) ion, and a linear multifunctional ligand 3-nitro-4,4'-biphenyldicarboxylic acid, formulated as {[Y(μ3-OH)]4[Y(μ3-OH)(μ2-H2O)0.25(H2O)0.5]4[μ4-nba]8}n (1), where H2nba = 3-nitro-4,4'-biphenyldicarboxylic acid, has been hydrothermally synthesized and characterized through infrared spectroscopy (IR), elemental and thermal analysis (EA), power X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD) analyses. X-ray diffraction structural analysis revealed that 1 crystallizes in tetragonal system with P4¯21m space group, and features a 3D framework with 1D square 18.07(3)2 Å2 channels running along the [0,0,1] or c-axis direction. The structure of 1 is built up of unusual eight-membered rings formed by two types of {Y4O4} clusters connected to each other via 12 μ4-nba2- and 4 μ3-OH- ligands. Three crystallographic independent Y3+ ions display two coordinated configurations with a seven-coordinated distorted monocapped trigonal-prism (YO7) and an eight-coordinated approximately bicapped trigonal-prism (YO8). 1 is further stabilized through O-H⋯O, O-H⋯N, C-H⋯O, and π⋯π interactions. Topologically, MOF 1 can be simplified as a 12-connected 2-nodal Au4Ho topology with a Schläfli symbol {420·628·818}{43}4 or a 6-connected uninodal pcu topology with a Schläfli symbol {412·63}. The fluorescent sensing application of 1 was investigated to cations and anions in H2O. 1 exhibits good luminescence probing turn-on recognition ability toward F- and with a limit detection concentration of F- down to 14.2 μM in aqueous solution (Kec = 11403 M-1, R2 = 0.99289, σ = 0.0539). The findings here provide a feasible detection platform of LnMOFs for highly sensitive discrimination of F- in aqueous media.

Dataset Information

Dual stimuli-induced formation of a ?-hydroxido bridged [Zn₉L₅(?-OH)₆]¹²⁺ half-pipe.

Publications

Dual stimuli-induced formation of a μ-hydroxido bridged [Zn<sub>9</sub>L<sub>5</sub>(μ-OH)<sub>6</sub>]<sup>12+</sup> half-pipe.

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Dataset Information

Dual stimuli-induced formation of a ?-hydroxido bridged [Zn9L5(?-OH)6]12+ half-pipe.

Publications

Dual stimuli-induced formation of a μ-hydroxido bridged [Zn<sub>9</sub>L<sub>5</sub>(μ-OH)<sub>6</sub>]<sup>12+</sup> half-pipe.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dual stimuli-induced formation of a ?-hydroxido bridged [Zn₉L₅(?-OH)₆]¹²⁺ half-pipe.