Templated dynamic cryptophane formation in water

Givelet, Cécile; Sun, Jiazeng; Xu, Di; Emge, Thomas J.; Dhokte, Ashwini; Warmuth, Ralf

doi:10.1039/c1cc10510h

Cited by 68 publications

(45 citation statements)

References 24 publications

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“…[12] Cryptophanes were classically constructed by multistep organic syntheses; [13] however, some examples were obtained by self-assembly processes with hydrogen [14] and coordination bonds [15] and, in a broader sense, dynamic covalent bonds such as disulfide [16] and imine bonds. [17] In the latter case, cryptophanes were assembled in thermodynamic equilibrium conditions, and this represents a unique illustration of the use of external templates for their formation. Self-assembly processes also led to larger or topologically complex assemblies such as a nanocube, a nano-octahedron, and a triply interlocked [2]catenane.…”

Section: Introductionmentioning

confidence: 99%

The Stereoselective Self‐Assembly of Chiral Metallo‐Organic Cryptophanes

et al. 2016

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International audienceCryptophanes are macropolycyclic cyclophanes constructed from two triply bridged concave cyclotriveratrylene analogues that encapsulate a large range of molecular and monoatomic substrates. Self-assembled metallo-organic cryptophanes based on M2+–carbonitrile (M = Pd or Pt) interactions have been obtained through the reactions of chiral nitrile-substituted cyclotribenzylenes (CTBs) 1 and 2 with [M(dppp)][OTf]2 (dppp = 1,3-bisdiphenylphosphinopropane, OTf = triflate) in 2:3 ratios in chlorinated solvents. The cryptophanes [Pd3(dppp)3(1)2]6+ and [Pd3(dppp)3(2)2]6+ were obtained exclusively in the chiral anti form in solution at room temperature whatever solvent was used; however the meso,syn form was identified as the major isomer of [Pd3(dppp)3(1)2]6+ at low temperature in CD2Cl2, and – in the case of [Pt3(dppp)3(1)2]6+ – it formed in a minor amount at room temperature. [Pd3(dppp)3(1)2][OTf]6 and [Pt3(dppp)3(1)2][OTf]6 crystallized in the anti forms with an encapsulated chloroform molecule, and gas-phase DFT calculations with the dispersion-corrected B97-D3 functional show that it is stabilized by 34.6 kJ mol–1. Interestingly, the heteroleptic cryptophane [Pd3(dppp)3(1)(2)]6+ was not detected in mixtures of [Pd(dppp)]2+ and CTBs 1 and 2 in a 3:1:1 ratio or through the equilibration of a 1:1 mixture of the preformed homoleptic cryptophanes; this points to favored self-sorting processes

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Section: Introductionmentioning

confidence: 99%

The Stereoselective Self‐Assembly of Chiral Metallo‐Organic Cryptophanes

et al. 2016

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“…One of the versatile methods is the reversible Schiff base condensation between an amine and aldehyde, which falls within the familiar domain called dynamic covalent chemistry (DCC). A variety of organic cage compounds containing imine bonds with conformational rigidity have been reported in high yields by this method [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44].…”

Section: Introductionmentioning

confidence: 99%

Self assembled macrobicycle and tricycle cages containing pyrrole rings by dynamic covalent chemistry method

Jana

Das

Mani

2015

J Incl Phenom Macrocycl Chem

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Synthesis of discrete macrobicycle and oligocycle molecules with three dimensional cavities in high yields remains very important because of their potential applications in the area of molecular recognition. Dynamic covalent chemistry method has effectively been used to synthesize such molecules. The Schiff base condensation reaction between tris(a-formylpyrrolyl-a 0 -methyl)amine and ethylenediamine readily afforded the large size [2 ? 3] macrobicycle in very high yield. The analogous reaction between this trialdehyde and tris(2-aminoethyl)amine gave the [2 ? 2] macrotricycle Schiff base in good yield. Subsequent reduction reactions using sodium borohydride yielded the corresponding saturated products in good yields. The anion binding ability of the [2 ? 3] saturated macrobicycle was explained through the X-ray structure of the chloride anion encapsulated complex.

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“…Hemicarcerands allow guests to enter and exit the cavity at high temperatures, however they form stable complexes at ambient temperatures [4]. Over the last 30 years a great deal of research has been conducted aiming to create small, large, and of adjustable size covalent capsules and with a variety of solubilities [5][6][7][8][9]. Encapsulation enables rigorous control of environment and the encounters of molecules isolating them from solvent encounters at ambient temperatures in the liquid phase [10].…”

Section: Introductionmentioning

confidence: 99%