Self-Assembly of 2,8,14,20-Tetraisobutyl-5,11,17,23-tetrahydroxyresorc[4]arene

Gerkensmeier, Thorsten; Iwanek, Waldemar; Agena, Ceno; Fröhlich, Roland; Kotila, Sirpa; Näther, Christian; Mattay, Jochen

doi:10.1002/(sici)1099-0690(199909)1999:9<2257::aid-ejoc2257>3.3.co;2-8

Cited by 100 publications

(182 citation statements)

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“…Pyrogallol[4]arenes are a subclass of calix[4]arenes with bowl‐like shape and hydroxy functional groups. The synthetic method for pyrogallol[4]arenes is similar to that for calixarenes, by condensation of pyrogallol with aldehydes . Because of their favorable cyclic shape, 12 hydroxyl groups and high polarity, pyrogallol[4]arenes have been used extensively as starting materials for carcerand synthesis, and self‐assembly to molecular vesicles, capsules, and other supramolecular architectures .…”

Section: Pyrogalloarene‐based Comsmentioning

confidence: 99%

Supramolecular‐Macrocycle‐Based Crystalline Organic Materials

et al. 2019

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macrocycles. They have been also employed to modify the surface properties of metal nanoparticles via noncovalent host−guest interactions, [31] covering their applications in drug delivery, [32] highly sensitive sensors, [33] selective catalysis, [34] and so on.In addition to their intensive applications based on their host−guest chemistry, macrocycles have also been used as building blocks to construct solid materials including porous organic polymers (POPs), [35,36] metal-organic frameworks (MOFs), [37][38][39][40][41][42][43] and crystalline organic materials (COMs). [44][45][46][47][48][49][50][51][52][53][54][55][56][57] Particular attention should be paid to COMs, a class of organic materials featuring facile preparation, high crystallinity, structural diversity, chemical stability, solution-processability, etc. [58][59][60][61][62][63][64][65][66][67][68][69][70] Different from MOFs that are composed of both inorganic (metal ions) and organic species (organic ligands) through coordination, COMs refer to a kind of crystalline materials composed of pure organics connected by either covalent or noncovalent bonds. [71][72][73] For COMs connected by noncovalent bonds, the typical materials are organic molecular crystals with intriguing properties such as semiconductor, [53] porosity, [68] etc. Owing to the inefficient packing of organic building blocks in the crystal state, some molecular crystals display extrinsic porosity, which are often termed as hydrogen-bonded organic frameworks (HOFs) [74,75] or supramolecular organic frameworks (SOFs). [76][77][78][79][80] For COMs connected by covalent bonds, typical materials are crystalline covalent organic frameworks (COFs), which were firstly reported in 2005 by Yaghi and co-workers [44] Benefitting from rigid chemical bonds and building blocks, COFs show permanent and well-ordered porosity. [45][46][47][48] Supramolecular-macrocycle-based COMs, a class of COMs with macrocycles as the main building blocks, have drawn particular attention in recent years. According to their components, supramolecular-macrocycle-based COMs can be classified into two main categories, the ones composed of pure macrocycles and the others consisting of macrocycles and other simple organic building blocks. Owing to their prefabricated cavities of a certain type, some of macrocycle-based COMs exhibit intrinsic microporosity for guest adsorption in the solid state. On the other hand, the extrinsic porosity of some macrocyclebased COMs may form due to the inefficient packing of these rigid macrocyclic molecules in the crystalline state. In certain circumstances, both intrinsic and extrinsic microporosity can be created in a single lattice of a certain COM, thus leading to Supramolecular macrocycles are well known as guest receptors in supramolecular chemistry, especially host−guest chemistry. In addition to their wide applications in host−guest chemistry and related areas, macrocycles have also been employed to construct crystalline organic materials (COMs) owing to their particular structur...

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Section: Pyrogalloarene‐based Comsmentioning

confidence: 99%

Supramolecular‐Macrocycle‐Based Crystalline Organic Materials

et al. 2019

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“…Both N−H⋅⋅⋅O and C−H⋅⋅⋅O interactions are well‐known to occur in solid‐state structures of isatins with typical N⋅⋅⋅O distances of 2.79–2.91 Å and typical C⋅⋅⋅O distances of 3.14–3.74 Å . The calculated cavity volume of capsule (+)‐( P )‐ 1 8 is about 2300 Å 3 , which is significantly larger than the calculated volumes of roughly 1400 Å 3 for hexameric resorcinarene‐ and pyrogallolarene‐derived capsules ,. Furthermore, the cavity volume is completely isolated from its surrounding with the exception of the windows defined by the cyclic N−H⋅⋅⋅O hydrogen‐bond arrays (ca.…”

Section: Figurementioning

confidence: 77%

“…One major difficulty in the synthesis of large noncovalently bound capsules arises from the relatively poor directionality of noncovalent interactions which can result in the formation of networks instead of discrete nanosized objects . In this regard, a simple way to reduce the likelihood of network formation is to design small molecules that form dimeric capsules through multiple interactions, and it is therefore not surprising that dimeric capsules far outnumber tetrameric, pentameric, hexameric,, and higher‐order capsules . However, a major drawback of this approach is that the size of the molecular units required for the construction of a dimeric capsule increases at the same rate as the targeted capsule itself.…”

Section: Figurementioning

confidence: 99%

Chirality‐Assisted Synthesis of a Very Large Octameric Hydrogen‐Bonded Capsule

2016

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The strategy of chirality-assisted synthesis, which makes use of enantiomerically pure building blocks that are designed to associate in a single geometric orientation, was applied to synthesize an octameric hydrogen-bonded capsule with a cavity volume of 2300 3 . This cube-shaped capsule forms even host-guest complexes with tetraalkylammonium ions, and accommodates the large tetrahexadecylammonium cation in its cavity. The use of an enantiopure building block was shown to be highly beneficial for capsule formation, whereas its racemate also generates a large amount of illdefined aggregates in solution and crystallizes as a hydrogenbonded network.The synthesis of artificial viral capsids self-assembled from small molecules has attracted considerable interest since the first molecular containers were reported by the groups of Cram [1] and Collet [2] in the mid-1980s. [3] Since then, the size of covalent organic [4] and metal-organic [5] cages has continuously increased, with the largest yet reported reaching a diameter of about 8 nm while partially surrounding an open cavity volume of roughly 160 000 3 . [6] In contrast, the size of closed-shell molecular capsules that spontaneously self-assemble in solution through noncovalent interactions has stagnated since hexameric resorcinarene-and pyrogallolarene-derived capsules were discovered in the late 1990s. [7] Such capsules completely enclose the space defined by their cavity, but with cavity volumes only reaching about 1400 3 they are dwarfed by even the smallest known viruses. As such, the encapsulation of large molecules (e.g., proteins and DNA fragments) by noncovalent capsules remains a long-term objective. [8] One major difficulty in the synthesis of large noncovalently bound capsules arises from the relatively poor directionality of noncovalent interactions which can result in the formation of networks instead of discrete nanosized objects. [9] In this regard, a simple way to reduce the likelihood of network formation is to design small molecules that form dimeric capsules through multiple interactions, and it is therefore not surprising that dimeric capsules [3f, 10] far outnumber tetrameric, [11] pentameric, [12] hexameric, [7a,b, 13] and higher-order capsules.[14] However, a major drawback of this approach is that the size of the molecular units required for the construction of a dimeric capsule increases at the same rate as the targeted capsule itself. From a synthetic point of view, it is far more desirable to use several small components instead of two large ones. The strategy of chirality-assisted synthesis may help solve this problem as the use of enantiopure, inherently chiral building blocks should work against the formation of polymeric materials.[15] Herein we show that this strategy can be exploited to rationally design a small molecule that predictably self-assembles into a hydrogen-bonded capsule with a very large cavity volume.Tris(isatin) 1 (Figure 1 A) was designed by combining a tribenzotriquinacene core [16] with confor...

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“…Six molecules of C ‐methylresorcin[4]arene ( 1 ) and eight molecules of water self‐assemble into a purely organic spheroid of nanometer dimensions that is stabilized by a large number of hydrogen‐bonding interactions between the hydroxy groups on the upper rim of the calixarene units and water molecules at the seams of the nanospheroid 9. Mattay and co‐workers described the self‐assembly of C ‐isobutylpyrogallol[4]arene into a hexameric capsule arrangement which is reminiscent of that formed with 1 10. Some of our recent work has focused on the organization of guest molecules with nanospheroids composed of C ‐alkylpyrogallol[4]arenes 2 whilst also establishing quantitative and reproducible recrystallization procedures from a particular solvent (ethyl acetate) 11.…”

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confidence: 99%

Toward the Isolation of Functional Organic Nanotubes

2006

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The last straw: Sonication of C‐hexylpyrogallol[4]arene with pyrene, acetonitrile, and water results in the formation of crystalline organic nanotubes. Alternating pockets of acetonitrile and water are contained within the large internal diameter of the tube formed by the calixarenes (see picture; the tube and solvent molecules are shown as stick and space‐filling representations, respectively).

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Self-Assembly of 2,8,14,20-Tetraisobutyl-5,11,17,23-tetrahydroxyresorc[4]arene

Cited by 100 publications

References 0 publications

Supramolecular‐Macrocycle‐Based Crystalline Organic Materials

Supramolecular‐Macrocycle‐Based Crystalline Organic Materials

Chirality‐Assisted Synthesis of a Very Large Octameric Hydrogen‐Bonded Capsule

Toward the Isolation of Functional Organic Nanotubes

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