Shape‐Persistent Organic Cage Compounds by Dynamic Covalent Bond Formation

Mastalerz, Michael

doi:10.1002/anie.201000443

Cited by 405 publications

(118 citation statements)

References 127 publications

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“…1c). 3 POCs are rigid molecules with a permanent internal void that is accessible to guests via 'windows' in the cage. [17][18][19] Control of structure and function for POCs can be difficult, however, because slight changes in the molecular structure 19 or the crystallization solvent 20 can cause a profound change in the crystal packing.…”

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confidence: 99%

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

et al. 2016

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Synthetic control over pore size and pore connectivity is the crowning achievement for porous metal-organic frameworks. The same level of control has not been achieved for molecular crystals, which are not defined by strong, directional intermolecular coordination bonds. Hence, molecular crystallization is inherently less controllable than framework crystallization, and there are fewer examples of 'reticular synthesis'-where multiple building blocks can be assembled according to a common assembly motif.Here, we apply a chiral recognition strategy to a new family of tubular covalent cages, to create both 1-D porous nanotubes and 3-D diamondoid pillared porous networks.The diamondoid networks are analogous to metal-organic frameworks prepared from tetrahedral metal nodes and linear, ditopic organic linkers. The crystal structures can be rationalized by computational lattice energy searches, which provide an in silico screening method to evaluate candidate molecular building blocks. These results are a blueprint for applying the 'node and strut' principles of reticular synthesis to molecular crystals.Despite many advances in supramolecular chemistry, it is still challenging to control molecular crystallization to create a specific, useful property. 1,2 This is important in the emerging area of porous molecular solids, 3 which have practical advantages such as solution processability. The crystal packing in porous molecular crystals defines the pore dimensions, which in turn define properties such as guest selectivity. 4,5 The same challenge-control over solid state structure-applies to all 2 functional molecular crystals because crystal packing defines physical properties such as electronic band gap and thermal or electrical conductivity.A central paradigm in crystal engineering is to synthesize building blocks, or 'tectons', with strong, directional interactions, such as hydrogen bonding 6 or metal-ligand binding, 7 which direct assembly into a targeted three-dimensional superstructure (Fig. 1). 1,2,8,9 For metal-organic frameworks (MOFs) and porous coordination polymers (PCPs), directional metal-ligand bonds are used to do this (Fig. 1a). [10][11][12][13][14] Likewise, hydrogen bonding can be used to create organic molecular crystals with defined network structures (Fig. 1b). 9,15,16 We have used chiral recognition to assemble porous organic cages 3 (POCs) into structures with 3-D pore channels (Fig. 1c). 3 POCs are rigid molecules with a permanent internal void that is accessible to guests via 'windows' in the cage. [17][18][19] Control of structure and function for POCs can be difficult, however, because slight changes in the molecular structure 19 or the crystallization solvent 20 can cause a profound change in the crystal packing. Chiral window-towindow interactions (Fig. 1e,f) can direct these POCs to assemble into 3-D pore networks in several cases, 19,21,22 but this is not ubiquitous. For example, some cages require specific solvents to template the window-to-window packing. 20 The chiral cage CC3-S (...

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Reticular synthesis of porous molecular 1D nanotubes and 3D networks

et al. 2016

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“…Organic cage molecules with three dimensional cavities containing functional groups remain an emerging field of research because of their applications in several areas [1][2][3][4][5][6][7][8]. Such cage molecules have been reported to recognize several analytes such as carbohydrate [9,10], hydrocarbons [11] and anions [12][13][14][15][16][17][18][19][20], and have also been demonstrated for applications such as gas sorption [21][22][23][24], separation [25,26] and sensing [27,28].…”

Section: Introductionmentioning

confidence: 98%

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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“…Boronic acids and esters are key materials in the areas of organic synthesis 1-3 , catalysis 4-6 , materials science 7,8 , drug discovery 9-11 , molecular self-assembly 12,13 , carbohydrate analysis 14-16 , and molecular sensing 17-20 . Photoinduced dissociation of Ar–X bonds has enabled a number of synthetically useful carbon–carbon and carbon–heteroatom bond-forming transformations, e.g.…”

Section: Introductionmentioning

confidence: 99%

Metal- and additive-free photoinduced borylation of haloarenes

et al. 2017

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Boronic acids and esters have crucial roles in the areas of synthetic organic chemistry, molecular sensors, materials science, drug discovery, and catalysis. Many of the current applications of boronic acids and esters require materials with very low levels of transition metal contamination. Most of the current methods for the synthesis of boronic acids require, however, transition metal catalysts and ligands that have to be removed via additional purification procedures. This protocol describes a simple, metal- and additive-free method of conversion of haloarenes directly to boronic acids and esters. This photoinduced borylation protocol does not require expensive and toxic metal catalysts and ligands and produces innocuous and easy-to-remove by-products. Furthermore, the reaction can be carried out on multigram scales in common grade solvents without the need for reaction mixtures to be deoxygenated. The setup and purification steps are typically accomplished within 1–3 h. The reactions can be run overnight, and the protocol can be completed within 13–16 h. Two representative procedures that are described in this protocol provide details for preparation of a boronic acid (3-cyanopheylboronic acid) and a boronic ester (1,-benzenediboronic acid bis(pinacol)ester). We also discuss additional details of the method that will be helpful in the application of the protocol to other haloarene substrates.

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Shape‐Persistent Organic Cage Compounds by Dynamic Covalent Bond Formation

Cited by 405 publications

References 127 publications

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

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

Metal- and additive-free photoinduced borylation of haloarenes

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