Use of hydrogen bonds to control molecular aggregation. Self-assembly of three-dimensional networks with large chambers

Simard, Michel; Su, Dan; Wuest, James D.

doi:10.1021/ja00012a057

Cited by 816 publications

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“…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).…”

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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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“…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).…”

mentioning

confidence: 99%

“…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).…”

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confidence: 99%

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

et al. 2016

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“…In these cases, porosity may not be obvious from inspection of the isolated molecular structure 24 . Crystal engineering approaches have been used to control the assembly of extrinsically porous molecular solids, for example using directional interactions such as hydrogen bonding [27][28][29] . A major practical problem for both intrinsically and extrinsically porous molecular crystals is that they often cannot be desolvated while retaining long-range molecular order.…”

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confidence: 99%

“…There has been less focus here in comparison with the preparation of ordered porous solids using crystal engineering [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] . Polymers of intrinsic microporosity (PIMs), for example, form amorphous microporous solids-that is, amorphous solids with pore dimensions smaller than 2 nm-as a result of their rigid and contorted chain structures 30,31 .…”

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Porous organic molecular solids by dynamic covalent scrambling

Jiang¹,

Jones²,

Hasell³

et al. 2011

Nat Commun

182

189

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The main strategy for constructing porous solids from discrete organic molecules is crystal engineering, which involves forming regular crystalline arrays. Here, we present a chemical approach for desymmetrizing organic cages by dynamic covalent scrambling reactions. This leads to molecules with a distribution of shapes which cannot pack effectively and, hence, do not crystallize, creating porosity in the amorphous solid. The porous properties can be fine tuned by varying the ratio of reagents in the scrambling reaction, and this allows the preparation of materials with high gas selectivities. The molecular engineering of porous amorphous solids complements crystal engineering strategies and may have advantages in some applications, for example, in the compatibilization of functionalities that do not readily cocrystallize.

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“…[2][3][4][5][6] We have been interested for some time in the synthesis and crystal structures of TeX 3 R compounds and their derivatives, such as the [TeX 4 R] -anions. These halogenated tellurates may be considered tectons (any species whose interactions are dominated by particular associative forces that induce the self-assembly of an organized network with specific architectural or functional features 7 ) where the different packing arrangements in the crystal lattice of [TeX 4 R] -salts are determined by the secondary bonds which complete the octahedral coordination at tellurium. We have already observed this tendency in a great number of examples with cations of alkali metals or pyridonium and ammonium derivatives.…”

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Synthesis and crystal structures of new complex salts containing both cationic and anionic tellurium(IV) species: the role of secondary bonds in the arrangement of tellurium based tectons

Santos¹,

Lang²,

Burrow³

2006

J. Braz. Chem. Soc.

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Neste trabalho divulgamos a síntese e a estrutura cristalina de uma série de três novos complexos de telúrio(IV), [Te(C 6 H 5 )(CH 3 ) 2 ]][TeX 4 (C 6 H 5 )], X = Cl (1), Br (2) ou I (3). Nesses complexos, as ligações secundárias promovem diferentes arranjos estruturais, mostrando o caráter tectônico das espécies de telúrio. Em 1 e 2, a interação Te···X promove um arranjo polimérico na forma de "zig-zag" para os ânions tetra-halofeniltelurato(IV). Em 3, as ligações secundárias Te···I induzem um arranjo diferenciado para os ânions, que estão organizados de forma antiparalela.We report herein the synthesis and the crystal structures of three new tellurium(IV) complexes, [Te(C 6 H 5 )(CH 3 ) 2 ]][TeX 4 (C 6 H 5 )], X = Cl (1), Br (2), I (3). In these complexes, the secondary bonds promote different structural arrangements due to the tectonic character of the tellurium species. In 1 and 2, the Te···X interactions create a polymeric "zig-zag" chain of the tetrahalo-phenyltellurate(IV) anions. In 3, the secondary Te···I bonds induce a different arrangement for the anions that are organized in a pseudo-dimeric antiparallel fashion.Keywords: organotellurium halides, tectonic tetrahalo-organyltellurates, secondary bonding IntroductionSeveral classes of organyltellurium halide compounds are known, including species of general formula TeX 3 R, TeX 2 R 2 and TeXR 3 (R=alkyl, aryl; X=Cl, Br, I). The solid state structures of the tellurium(IV) compounds are themselves very interesting owing to the occurrence of secondary tellurium-halogen bonds (Te···X), 1 which create exceptional supramolecular structures, leading to the formation of polymeric chains, dimeric structures, or monomers with fairly strong intermolecular interactions. [2][3][4][5][6] We have been interested for some time in the synthesis and crystal structures of TeX 3 R compounds and their derivatives, such as the [TeX 4 R] -anions. These halogenated tellurates may be considered tectons (any species whose interactions are dominated by particular associative forces that induce the self-assembly of an organized network with specific architectural or functional features 7 ) where the different packing arrangements in the crystal lattice of [TeX 4 R] -salts are determined by the secondary bonds which complete the octahedral coordination at tellurium. We have already observed this tendency in a great number of examples with cations of alkali metals or pyridonium and ammonium derivatives. [8][9][10][11] We now report the synthesis and crystal structures of [Te(C 6 H 5 ) (CH 3 ) 2 ][TeX 4 (C 6 H 5 )], X = Cl (1), Br (2) and I (3), complexes in which organyltellurium(IV) ion is found in both anionic and cationic species. ExperimentalAll reactions were conducted under nitrogen, but recrystallizations of the complexes were done in air. Methanol was dried with Mg/I 2 and acetonitrile with CaH 2 , and both were distilled prior to use. 12 The compound iododimethylphenyltellurium(IV) was prepared according to Reid's procedure; 13 the analogous chloride and bromide derivatives...

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Use of hydrogen bonds to control molecular aggregation. Self-assembly of three-dimensional networks with large chambers

Cited by 816 publications

References 0 publications

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

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

Porous organic molecular solids by dynamic covalent scrambling

Synthesis and crystal structures of new complex salts containing both cationic and anionic tellurium(IV) species: the role of secondary bonds in the arrangement of tellurium based tectons

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