Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

Choi, Eun‐Young; Gao, Chunxia; Lee, Suck-Hyun; Kwon, O‐Pil

doi:10.5012/bkcs.2012.33.4.1264

Cited by 2 publications

(1 citation statement)

References 30 publications

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“…All reagents and solvents were purchased from Sigma-Aldrich and Alfa-Aesar. Syntheses of the azacryptand L and of the dicarboxylic acids H 2 1 –H 2 5 (Chart ) , have been reported elsewhere, whereas details on both the preparation and characterization of Na 2 2 –Na 2 5 are reported in the Supporting Information. Mass spectrometry (MS) spectra were acquired on a Thermo-Finnigan ion trap LCQ Advantage Max instrument equipped with an electrospray ionization (ESI) source and NMR spectra on a Bruker AVANCE 400 spectrometer (operating at 9.37 T, 400 MHz).…”

Section: Methodsmentioning

confidence: 99%

Self-Assembly of Pseudorotaxane Structures from a Dicopper(II) Molecular Cage and Dicarboxylate Axles

et al. 2018

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In this work, we employed for the first time a dinuclear bis[tris(2-aminoethyl)amine] cryptate to obtain the self-assembly of pseudorotaxane structures in an aqueous solution. The goal was achieved by exploiting the well-known affinity of the dicopper azacryptate with diphenyl spacers for the terephthalate anion. In particular, a series of molecular threads were synthesized by appending either alkyl or polyoxyethylene chains on both sides of the terephthalate benzene ring. The obtained dicarboxylic acids were precipitated as sodium salts, and their affinity toward the dicopper azacryptate was determined in a methanol/water mixture (pH 7). Experimental investigations showed that the chains' length and nature have a small impact on the 1:1 binding constants, whose values range between 4.98 and 5.18 log units. Computational studies indicated that the molecular axle is threaded through the azacryptate cavity, with the terephthalate group wedged between the two copper ions, coordinating both of them in the apical position (the one that, in the free azacryptate, is occupied by a water molecule). Compared to the inclusion complex with the plain terephthalate anion, a slight strain was found in the pseudorotaxane structure, induced by the inner chain of the thread inside the cavity. These results may be of great interest in all of the fields of science and technology in which host-guest recognition and molecular cages are applied.

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Section: Methodsmentioning

confidence: 99%

Self-Assembly of Pseudorotaxane Structures from a Dicopper(II) Molecular Cage and Dicarboxylate Axles

et al. 2018

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Single Crystals of a 2-Dimensional Metal Coordination Polymer Containing Pendant Carbazole Groups

Choi¹,

Lee²,

Yun³

et al. 2013

Bulletin of the Korean Chemical Society

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Coordination polymers consisting of metal cations and organic linkers are widely used in fundamental supramolecular approaches as well as various other practical applications. [1][2][3][4] There are various types of metal-organic coordinated structures 2,5,6 such as linear-shaped 1-dimensional (1D), 7,8 sheet-shaped 2-dimensional (2D) 9,10 and networkshaped 3-dimensional (3D) 11,12 structures.Such coordinated structures are dependent on the substituents that are present on the organic linkers. For example, the organic linker H 2 BDC (benzene-1,4-dicarboxylic acid or terephthalic acid) formed a 3D metal-organic framework (MOF) structure with a well-defined cavity, with zinc cations. 11 H 2 BDC analogues that had small substituents (e.g., Br, NH 2, and short alkoxy chains) with volumes that are smaller than the cavity volume, also formed similar 3D MOF structures. 13,14 In contrast, the presence of more bulky substituents results in the formation of 3D MOF or 1D coordinated structures. For example, 2,5-disubstituted H 2 BDC analogues, in which the substituents were long alkoxy chains-like octyloxy chains, first formed a 3D MOF structure that then transferred to a 1D coordinated structure. [15][16][17] When more bulky substituents such as 3-(9H-carbazol-9-yl)octyloxy groups were introduced on a H 2 BDC linker, only 1D coordinated structure was obtained. 18 In this work, we studied a novel metal coordination polymer based on an organic H 2 BDC analogue, in order to determine the influence of the substituents of the organic linker on metal coordinated structure. In contrast to previous reports, 15,18 the organic linker 2,5-bis(3-(9H-carbazol-9-yl)-propoxy)benzene-1,4-dicarboxylic acid (CZ3-acid, see Figure 1) having bulky carbazole groups formed single crystals resulting from sheet-shaped 2D metal coordinated structure. Therefore, the coordinated structure was strongly dependent on the size of the substituents on the H 2 BDC linkers.Our novel metal coordination polymer was composed of zinc cations and a H 2 BDC analogue. Figure 1 shows the chemical structure of the organic linker CZ3-acid, which is a H 2 BDC analogue having 2,5-disubstituted groups. The bulky non-polar carbazole groups are connected by propyloxy spacers. The metal coordination polymer of CZ3-acid with zinc nitrate [Zn(NO 3 ) 2 ·6H 2 O] was synthesized by a solvothermal reaction in dimethylformamide (DMF). As shown in Figure 1, transparent single crystals of the metal coordination polymer were obtained directly from the solvothermal reaction.In order to understand the coordinated structure of the single crystals, we analyzed the crystal structure of the metal coordination polymer by X-ray single crystal structure analysis. The metal coordination polymer exhibited triclinic P-1 space group symmetry with high crystal quality as described in the Experimental section. The solvent DMF also participated in the crystal structure. These crystals are henceforth denoted as "[Zn(CZ3)(DMF)]".In general, many metal coordination polymers that contain solvents exhi...

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Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

Cited by 2 publications

References 30 publications

Self-Assembly of Pseudorotaxane Structures from a Dicopper(II) Molecular Cage and Dicarboxylate Axles

Self-Assembly of Pseudorotaxane Structures from a Dicopper(II) Molecular Cage and Dicarboxylate Axles

Single Crystals of a 2-Dimensional Metal Coordination Polymer Containing Pendant Carbazole Groups

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