Anisotropic Movements of Coordination Polymers upon Desolvation: Solid‐State Transformation of a Linear 1D Coordination Polymer to a Ladderlike Structure

Nagarathinam, Mangayarkarasi; Vittal, Jagadese J.

doi:10.1002/ange.200600376

Cited by 23 publications

(2 citation statements)

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“…The cross peaks between the ortho protons of the phenyl substituent or the protons at С(1) and С(22) of the naphthyl substituent and the olefinic proton H β appears in the spectra of compounds 6 and 8 (n = 2), which is quite consistent with the trans S cis S cis trans conformation similar to the corresponding fragment of the molecules in crystals. In the 2D NOESY spectra of compounds 5 and 7 (n = 1), the ortho protons of the phenyl substituent and the protons at С(1) and С (19) of the naphthyl substituent give cross peaks with H β and H α of approximately equal intensity, indicating that the trans S trans S trans trans conformation is pre sent in solution and the conjugation of the aromatic cycle and double bond is partially distorted. A comparison of the X ray diffraction and NMR spectroscopic data for crownophanes 5 and 7 indicates the conformational trans formation of one rotamer into another upon dissolution.…”

Section: Resultsmentioning

confidence: 97%

Pre-organization of diarylideneacetonyl crownophanes in single crystals to photochemical transformations

et al. 2011

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Specific features of crystal packings and pre organization of diarylideneacetonyl crowno phane molecules to solid phase photochemical transformations were studied on the basis of X ray diffraction data using methods of simulation of molecular crystal packings. The tendency of the most part of the synthesized macrocyclic E,E isomers to the formation of homochiral crystals (Р2 1 2 1 2 1 ) was revealed, while (23E,26E) 11,12,14,15 tetrahydro 8H dinaphtho [2,1 k:1´,2´ r] [1,4,7,10]tetraoxacyclononadecine 23,26 dien 25(9H) one is prone to polymor phism. A phenomenon of solid phase stereospecific photochemical dimerization of molecules according to the syn head to tail type without crystal destruction (single crystal-single crystal transformation) was found for one of the modifications of this crownophane.

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Section: Resultsmentioning

confidence: 97%

Pre-organization of diarylideneacetonyl crownophanes in single crystals to photochemical transformations

et al. 2011

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“…owing to their easy-accessible high surface area, tunable pore functionality and structural flexibility123456789101112131415. Separation is one of the most important aspects in chemical industry.…”

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confidence: 99%

Framework-Flexibility Driven Selective Sorption of p-Xylene over Other Isomers by a Dynamic Metal-Organic Framework

Mukherjee

Joarder

Manna

et al. 2014

Sci Rep

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Chemical separation has great importance in industrial applications. Separation of xylene isomers still prevails to be one of the most important challenges in chemical industry, due to the large amount of commercial use of p-xylene in the production of beverage bottles, fibers and films. A novel Zn(II)-based dynamic coordination framework based on flexible ether-linkage, exhibiting selective adsorption of p-Xylene over its congener C8-alkyl aromatic isomers at ambient conditions is reported. Notably, no dynamic structure based MOF compound is known in the literature which shows clear preference of p-xylene over other isomers. This type of framework-breathing and guest-induced reversible solid-state structural transformations with unique adsorption selectivity can be exploited purposefully to develop smart functional host materials capable of industrially important chemical separations.

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Reversible Topochemical Transformation of a Soft Crystal of a Coordination Polymer

2007

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One of the goals of materials chemistry is the synthesis of crystalline compounds known as porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) that are built from organic ligands and metal ions.[1] Their frameworks are composed of a variety of structures ranging from onedimensional (1D), 2D, to 3D motifs depending on how the coordination bonds form. These compounds, which are lowdensity solids, can be tailored, and have potential use in gas storage, molecular sensing, and other materials applications. One of the most important discoveries in the area of PCPs is their flexible and dynamic properties, which are characteristic of the cooperative action of organic and inorganic moieties. [2, 3] Guest-responsive changes between the solid phases are particularly intriguing. Although various cases of structural transformation (single crystal to amorphous phase) are known, examples of single-crystal to single-crystal phase (SCSC) transformation [4][5][6] are still lacking. A low-dimensional (1D or 2D) framework has a structural freedom in regards to the metal ions, while a 3D framework is sufficiently rigid to prevent recombination of the coordination bonds around the metal ions. As the structures and properties of SCSC structural transformations are well characterized, they are highly suitable for study to gain a further understanding of their dynamic behavior. In particular, structural transformations involving 2D and 3D frameworks are most important because most of the coordination compounds with important properties-such as gas storage, separation, sensor, magnetism, and catalysis-are generally 3D frameworks, whereas 2D structures containing spaces between the layers have more dynamic properties. The exploration of such a transformation is significant because it can provide not only unique properties characteristic of 3D frameworks, but also external stimulus-responsive properties based on the 2D-3D transformation (Figure 1).Herein, we describe the synthesis of a 2D compound using tetramethylammonium chloride as a blocking agent [7] (to stop the formation of the 3D structure), a tridentate ligand having highly flexible arms, and lanthanide metal ions, which have variable and high coordination numbers, which can provide more structural freedom to facilitate the transformation to a 3D structure.Two isomorphous compounds, {[Ce(tci)(H 2 O) 2 ]·2 H 2 O} n (1) and {[Pr(tci)(H 2 O) 2 ]·2 H 2 O} n (2), were prepared by the hydrothermal technique using tris(2-carboxyethyl) isocyanurate (tciH 3 ) with Ln(NO 3 ) 3 ·x H 2 O in the presence of tetramethylammonium chloride. The compounds once formed are insoluble in most solvents, including H 2 O. The structure of 1 is shown in Figure 2. The asymmetric unit consists of one Ce III center, one molecule of tci, and two types of H 2 O moleculestwo bound to Ce ions and two free in the channel. Each Ce III ion is surrounded by eight oxygen atoms, two of the oxygen atoms being from the water molecules and the rest come from the tci unit to give an overall distorted sq...

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Anisotropic Movements of Coordination Polymers upon Desolvation: Solid‐State Transformation of a Linear 1D Coordination Polymer to a Ladderlike Structure

Cited by 23 publications

References 54 publications

Pre-organization of diarylideneacetonyl crownophanes in single crystals to photochemical transformations

Pre-organization of diarylideneacetonyl crownophanes in single crystals to photochemical transformations

Framework-Flexibility Driven Selective Sorption of p-Xylene over Other Isomers by a Dynamic Metal-Organic Framework

Reversible Topochemical Transformation of a Soft Crystal of a Coordination Polymer

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