Recent Advances in Tris‐Primary Amine Based Organic Imine Cages and Related Amine Macrocycles

Gayen, Krishnanka S.; Das, Tapan Kumar; Chatterjee, Nirbhik

doi:10.1002/ejoc.202001194

Cited by 13 publications

(8 citation statements)

References 58 publications

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“…These features, which are also maintained after reduction to the amino form, are employed by several groups to enhance the cage selectivity towards guest molecules in solution. A number of bistren azacryptands (in particular polyimine systems) has also been reported as solid materials for the electrochemical reduction of CO 2 to CO and for CO 2 sequestration processes from multicomponent gas streams [ 29 , 30 , 31 ]. However, as far as we know, this particular class of molecules has never been tested in MMMs.…”

Section: Introductionmentioning

confidence: 99%

PEEK–WC-Based Mixed Matrix Membranes Containing Polyimine Cages for Gas Separation

et al. 2021

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Membrane-based processes are taking a more and more prominent position in the search for sustainable and energy-efficient gas separation applications. It is known that the separation performance of pure polymers may significantly be improved by the dispersion of suitable filler materials in the polymer matrix, to produce so-called mixed matrix membranes. In the present work, four different organic cages were dispersed in the poly(ether ether ketone) with cardo group, PEEK-WC. The m-xylyl imine and furanyl imine-based fillers yielded mechanically robust and selective films after silicone coating. Instead, poor dispersion of p-xylyl imine and diphenyl imine cages did not allow the formation of selective films. The H2, He, O2, N2, CH4, and CO2 pure gas permeability of the neat polymer and the MMMs were measured, and the effect of filler was compared with the maximum limits expected for infinitely permeable and impermeable fillers, according to the Maxwell model. Time lag measurements allowed the calculation of the diffusion coefficient and demonstrated that 20 wt % of furanyl imine cage strongly increased the diffusion coefficient of the bulkier gases and decreased the diffusion selectivity, whereas the m-xylyl imine cage slightly increased the diffusion coefficient and improved the size-selectivity. The performance and properties of the membranes were discussed in relation to their composition and morphology.

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Section: Introductionmentioning

confidence: 99%

PEEK–WC-Based Mixed Matrix Membranes Containing Polyimine Cages for Gas Separation

et al. 2021

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“…In addition to the selected examples of the above-described [2 + 3] cages, tris-primary amines, aliphatic and aromatic, have been extensively used to prepare cage structures. Some of these triamines are commercially available and others can be prepared by following the synthetic protocols in the literature . Zhang and co-workers showed that a complementary geometry between triamine 131 (planar) or 132 (pyramidal) and dialdehydes 133 – 138 is key for obtaining cage structures.…”

Section: Cages and Containers Soluble In Organic Solvents And Their A...mentioning

confidence: 99%

Purely Covalent Molecular Cages and Containers for Guest Encapsulation

et al. 2022

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Cage compounds offer unique binding pockets similar to enzyme-binding sites, which can be customized in terms of size, shape, and functional groups to point toward the cavity and many other parameters. Different synthetic strategies have been developed to create a toolkit of methods that allow preparing tailor-made organic cages for a number of distinct applications, such as gas separation, molecular recognition, molecular encapsulation, hosts for catalysis, etc. These examples show the versatility and high selectivity that can be achieved using cages, which is impossible by employing other molecular systems. This review explores the progress made in the field of fully organic molecular cages and containers by focusing on the properties of the cavity and their application to encapsulate guests.

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“…According to our previously reported work, the iminocontaining superphane 7a could be accessible via dynamic self-assembly of hexakis-amine (5) and m-phthalaldehyde (6a) in a 2:6 ratio in one pot. 32 Inspired by the fact that macrobicyclic azacryptands and sandwich-like azacyclophanes could be easily prepared through reversible and thermodynamically driven imine condensation, followed with a reduction step, [34][35][36] we next sought to transform imine superphane 7a into its stable amine form. To our delight, treatment of 7a with NaBH4 in a mixture of CH2Cl2 and CH3OH (1:1, v/v) at room temperature over 5 h led to the formation of amine superphane 3a in 81% yield (Scheme 1).…”

Section: One-pot Gram-scale Synthesis and Pre-modificationmentioning

confidence: 99%

Superphanes: Facile and Efficient Preparation, Functionalization and Unique Properties

Liu

Zhou

et al. 2021

Preprint

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Superphanes, compounds in which the two benzene rings clamped parallel on top of each other by six bridges, have garnered considerable interest due to their aesthetically pleasing structures and unique chemical physical properties. However, until now progress in the research of superphane chemistry and beyond has been seriously hampered by their poor availability. Herein, we report the facile and scalable synthesis of a collection of superphanes with structural diversity and their unique photophysical properties, as well as their unusual host–guest behavior. Initially, a set of dodecaimino–containing super-phanes 7a–7e are obtained via dynamic self–assembly of a hexakis–amine and a series of readily derived aromatic dialde-hyde in one pot. The resulting superphanes are found capable of being reduced with NaBH4 to their corresponding second-ary–amine versions 3a–3e. Subsequently, superphane 3c bearing 12 amine–NHs was further subject to post–functionalization with various functional groups, e.g., ethyl, allyl, propargyl and but–2–yn–1–yl. Unprecedentedly, the sec-ondary amine–based superphanes 3a–3e were observed to exhibit genuine fluorescence both in solution and in the solid state while the imine–based superphanes 7a–7e were found to highly emissive only in solid state with fluorescent quantum yields of 3.5 ~ 17.1. Finally, fully protonated 3a was exemplified to encapsulate a 2Cl–·H2O cluster both in the solid state and in solution. With the easy and versatile synthesis, modification, as well as unique photophysical and host–guest properties, we believe that this study will break the bottleneck in superphane chemistry and open the door to a novel class of supramo-lecular hosts and advanced functional materials on the basis of superphanes.

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Recent Advances in Tris‐Primary Amine Based Organic Imine Cages and Related Amine Macrocycles

Cited by 13 publications

References 58 publications

PEEK–WC-Based Mixed Matrix Membranes Containing Polyimine Cages for Gas Separation

PEEK–WC-Based Mixed Matrix Membranes Containing Polyimine Cages for Gas Separation

Purely Covalent Molecular Cages and Containers for Guest Encapsulation

Superphanes: Facile and Efficient Preparation, Functionalization and Unique Properties

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