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

Jana, Debasish; Das, Sanghamitra; Mani, Ganesan

doi:10.1007/s10847-015-0517-8

Cited by 4 publications

(5 citation statements)

References 75 publications

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“…118–122 In some cases, more than one anion is bound within a cage produced via DCC. One example comes from Jana et al 123 who reported the synthesis and structural characterization of macrobicycles and macrotricycles obtained via Schiff base condensations. The solid state structure of the chloride anion complex of the macrobicycle 83 in the protonated form revealed that the eight amine nitrogen atoms of the neutral bicycle molecule including the two bridgehead nitrogen atoms are fully protonated.…”

Section: Bicyclic Anion Receptorsmentioning

confidence: 99%

Supramolecular Chemistry of Anionic Dimers, Trimers, Tetramers, and Clusters

Sessler

2018

Chem

142

108

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Two or more anions constrained in close proximity within a single pocket are found in a number of natural systems but a less common motif in artificial systems. This review summarizes work on anion receptors capable of stabilizing anionic dimers, trimers, tetramers and clusters in a well-defined fashion. These systems may provide insights into the fundamental chemistry of anion-anion interactions and provide a guide for understanding in greater detail a number of biological and environmental processes, as well as key tenants of relevance to supramolecular chemistry, extraction, transport, crystal engineering, and the like. The primary goal of this review is to provide a general introduction into multi-anion recognition chemistry for the benefit of supramolecular and non-supramolecular chemists alike.

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Section: Bicyclic Anion Receptorsmentioning

confidence: 99%

Supramolecular Chemistry of Anionic Dimers, Trimers, Tetramers, and Clusters

Sessler

2018

Chem

142

108

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“…Starting in 2011, Mani et al reported a series of cages, compounds 9 – 14 given in Chart , − which were seen capable of binding a number of representative anions (e.g., F – , Cl – , Br – , NO 3 – , H 2 PO 4 – , and HSO 4 – ) in organic media such as CDCl 3 , DMSO- d 6 , and (CD 3 ) 2 CO under ambient conditions. A few representative X-ray structures of the resulting anion-bound cryptates are shown in Figure .…”

Section: Covalent Oligopyrrolic Macrobicyclic Cagesmentioning

confidence: 99%

Oligopyrrolic Cages: From Classic Molecular Constructs to Chemically Responsive Polytopic Receptors

Wang

Bucher

et al. 2022

Acc. Chem. Res.

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Conspectus “Functional molecular systems”, discrete and self-assembled constructs where control over molecular recognition, structure, bonding, transport, release, catalytic activity, etc., is readily achieved, are a topic of current interest. Within this broad paradigm, oligopyrrolic cages have garnered attention due to their responsive recognition features. Due to the presence of slightly polar pyrrole subunits which can also behave as hydrogen-bonding donors, these oligopyrrolic cages are potential receptors for various polarized species. In this Account, we summarize recent advances involving the syntheses and study of (1) covalent oligopyrrolic macrobicyclic cages, (2) oligopyrrolic metallacages, and (3) oligopyrrolic noncovalently linked cages. Considered in concert, these molecular constructs have allowed advances in applied supramolecular chemistry; to date, they have been exploited for selective guest encapsulation studies, anion binding and ion-channel formation, and gas absorption, among other applications. While key findings from others will be noted, in this Account will focus on our own contributions to the chemistry of discrete oligopyrrolic macrocycles and their use in supramolecular host–guest chemistry and sensing applications. In terms of specifics, we will detail how oligopyrrole cages with well-defined molecular geometries permit reversible guest binding under ambient conditions and how the incorporation of pyrrole subunits within larger superstructures allows effective control over anion/conjugate acid binding activity under ambient conditions. We will also provide examples that show how derivatization of these rudimentary macrocyclic cores with various sterically congested β-substituted oligopyrroles can provide entry into more complex supramolecular architectures. In addition, we will detail how hybrid systems that include heterocycles other than pyrrole, such as pyridine and naphthyridine, can be used to create self-assembled materials that show promise as gas-absorbing materials and colorimetric reversible sensors. Studies involving oligopyrrolic polymetallic cages and oligopyrrolic supramolecular cages will also be reviewed. First, we will discuss all-carbon-linked oligopyrrolic bicycles and continue on to present systems linked via amines and imines linkages. Finally, we will summarize recent work on pyrrolic cages created through the use of metal centers or various noncovalent interactions. We hope that this Account will provide researchers with an initial foundation for understanding oligopyrrolic cage chemistry, thereby allowing for further advances in the area. It is expected that the fundamental design and recognition principles made in the area of oligopyrrole cages, as exemplified by our contributions, will be of general use to researchers targeting the design of functional molecular systems. As such, we have structured this Account so as to summarize the past while setting the stage for the future.

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“…method. [26] The Schiff-base condensation reaction between tris(α-formylpyrrolyl-α'-methyl)amine 40 and ethylenediamine readily gave thermodynamically stable 41. Subsequent reduction reaction using sodium borohydride yielded corresponding saturated product 42 (Scheme 10).…”

Section: N Bridgeheadsmentioning

confidence: 99%

“…Mani and co-workers reported a large size macrobicycle 41 and its reduced product 42 by dynamic covalent chemistry (DCC) method. [26] The Schiff-base condensation reaction between tris(α-formylpyrrolyl-α'-methyl)amine 40 and ethylenediamine readily gave thermodynamically stable 41. Subsequent reduc- tion reaction using sodium borohydride yielded corresponding saturated product 42 (Scheme 10).…”

Section: N Bridgeheadsmentioning

confidence: 99%

“…Mani and co-workers first time reported a large macrotricyclic imino-pyrrolic molecule 44 and its reduced product 45 with good yields. [26] The [2 + 2] Schiff-base condensation reaction between tris(α-formylpyrrolyl-α'-methyl)amine 40 and tris(2aminoethyl)amine, (tren) generated a (18 + 18 + 36) membered tricyclic cage 44 (Scheme 11). The corresponding reduced product 45 was also isolated upon treatment of 44 with a hydride donor i. e. sodium borohydride.…”

Section: [2 Tris-amine + 2 Trialdehyde ] Typementioning

confidence: 99%

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Pyrrole‐Based Cryptand‐Like Cages: A Critical Overview of Synthetic Strategies and Applications

et al. 2022

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Pyrrole-based cryptand-like cages are important owing to their three-dimensional cavities together with three open crevices or clefts. The polar pyrrole subunits in the cages preorganize themselves to construct rigid and shape persistent molecular frameworks. Both the inner voids (cavity and cleft) are accessible to various guests such as metal ions, anions and, neutral molecules. The pyrrole ring offers hydrogen bond donor NH groups and its π-electrons to bind anions or neutral molecules, whereas sigma donation of pyrrolides stabilizes metal ions. In addition, the orientation of bridgehead positions of the cryptand molecules along with specific conformations of the pyrrole rings and/or connecting arms dictate the size of available void space which is directly related to the selectivity for specific guest molecules to be recognized. Thus, the cages have attracted attention in recent times for the development of supramolecular chemistry. In this review, we summarize different synthetic procedures of laterally symmetrical cryptand-like molecules, their structures, and applications in diverse aspects.

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

Cited by 4 publications

References 75 publications

Supramolecular Chemistry of Anionic Dimers, Trimers, Tetramers, and Clusters

Supramolecular Chemistry of Anionic Dimers, Trimers, Tetramers, and Clusters

Oligopyrrolic Cages: From Classic Molecular Constructs to Chemically Responsive Polytopic Receptors

Pyrrole‐Based Cryptand‐Like Cages: A Critical Overview of Synthetic Strategies and Applications

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