Tetraanionic Organoborate Squares Glued Together by Cations To Generate Nanotubular Stacks

Abrahams, Brendan F.; Price, David J.; Robson, Richard

doi:10.1002/ange.200503156

Cited by 18 publications

(6 citation statements)

References 4 publications

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“…The dynamic covalent [20] nature of both B À O and C=N bonds [21] allows both diol and amine subcomponents to be independently displaced within these structures in well-defined ways, allowing one structure to be transformed into another. This work thus applies the concepts of subcomponent self-assembly to the rich field of boron-based self-assembly, which includes such recent examples as chemosensors, [22] multicomponent architectures, [18] reversibly formed cages, [23] boroxoaromatics, [21] anionic borate assemblies, [24] borylferrocene structures, [25] macrocycles, [26] as well as self-repairing polymers [27] and porous networks. [28] …”

Section: Introductionmentioning

confidence: 99%

An Iminoboronate Construction Set for Subcomponent Self‐Assembly

Hutin

Bérnardinelli

Nitschke

2008

Chemistry A European J

122

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Recently we have demonstrated a series of systems in which complex structures were created from simple amine and aldehyde subcomponents by copper(I)-templated imine bond formation. We describe herein the extension of this "subcomponent self-assembly" concept to the generation of structures based upon the iminoboronate ester motif. Equimolar amounts of diol, amine, and 2-formylphenylboronic acid reacted by reversible B-O and C=N bond formation to generate iminoboronate esters, as has recently been reported by James et al. (Org. Lett. 2006, 8, 609-612). The extent of ester formation was shown to depend upon a number of factors. The exploration of these factors allowed rules and predictions to be formulated governing the self-assembly process. These rules allowed the construction of more complex structures containing multiple boron atoms, including a trigonal cage containing six boron centers, as well as pointing the way to the construction of yet more intricate architectures. The lability of the B-O and C=N bonds also allowed different diol and amine subcomponents to be substituted within these structures. Selection rules were also determined for these substitution reactions, allowing the products to be predicted based upon the electronic properties of the diols and diamines employed. These results thus demonstrate the generality of the subcomponent self-assembly methodology through its application to a new dynamic covalent system.

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Section: Introductionmentioning

confidence: 99%

An Iminoboronate Construction Set for Subcomponent Self‐Assembly

Hutin

Bérnardinelli

Nitschke

2008

Chemistry A European J

122

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“…It is well known that boronic esters can easily be prepared by mixing boronic acids and alcohols with azeotropic removal of water or in the presence of a dehydrating agent, and in favorable cases using 1,2-and 1,3-diols, cyclic boronic ester formation occurs spontaneously even in the absence of a dehydrating agent. [7,8] The overall process is an equilibrium, and this reversible reaction has previously been employed to build complex structures such as macrocycles, [9] dendrimers, [10] helicates, [11] nanotubes, [12] capsules, [13] porous covalent organic frameworks, [14] and polymers. [15] In a recent communication, [16] we reported that boronic ester formation can be used to achieve the dynamic selfassembly of organic molecules into macrocycles through dynamic covalent-bond formation.…”

Section: Introductionmentioning

confidence: 99%

Crystallization‐Controlled Dynamic Self‐Assembly and an On/Off Switch for Equilibration Using Boronic Ester Formation

Takahagi

Iwasawa

2010

Chemistry A European J

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Macrocyclic boronic esters of different sizes can be prepared selectively from the same starting diboronic acid and 1,2-diol by means of an interesting dynamic self-assembly phenomena. More specifically, two kinds of macrocyclic boronic esters could be formed diastereoselectively and nearly quantitatively under neutral conditions by the addition of an appropriate guest molecule that acts as a template. Although a mixture of tetrol 1 and di(boronic acid) 2 in methanol gave only insoluble polymeric boronic esters, a soluble macrocyclic boronic ester, homo-[2+2], was obtained selectively in the presence of toluene as a guest molecule. Furthermore, when benzene was employed as a guest molecule, the selective formation of another macrocyclic boronic ester, hetero-[3+3], occurred. Interestingly, each of these macrocycles could be converted into the other in the presence of methanol and the appropriate guest molecule; however, under aprotic conditions, guest molecules encaged by the macrocyclic boronic ester could be exchanged without affecting its structure. Thus the presence or absence of a protic solvent could be used as a regulator to switch on or off the dynamic equilibrium of the system. In addition, investigation of the effect of reaction time, direct observation of the reaction mixture by NMR spectroscopy, and carrying out the reaction using optically active tetrol suggested that precipitation plays an essentially important role in the selective formation of the macrocyclic boronic esters. Thus, although both of [2+2] and [3+3] were present as solutes in the reaction mixture, the type of added guest molecule induced the selective precipitation of only one form of macrocyclic boronic ester, hence displacing the equilibrium of the system.

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“…[9][10][11] The preparation of anionic supramolecular macrocycles was recently demonstrated by Robson and co-workers. [9][10][11] The preparation of anionic supramolecular macrocycles was recently demonstrated by Robson and co-workers.…”

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confidence: 99%

“…Although anionic cyclophanes are expected to exhibit better affinity toward electron-deficient guest compounds than the electrically neutral ones, only scattered attention has been given to the development of those cyclophanes. [9][10][11] The preparation of anionic supramolecular macrocycles was recently demonstrated by Robson and co-workers. [10] They mentioned that the self-organization of cyclic spiroborate was realized by the use of spirobisindane tetrols and trimethoxyborane as components.…”

mentioning

confidence: 99%

“…[9][10][11] The preparation of anionic supramolecular macrocycles was recently demonstrated by Robson and co-workers. [10] They mentioned that the self-organization of cyclic spiroborate was realized by the use of spirobisindane tetrols and trimethoxyborane as components. The selective construction of cyclic trimer and tetramer was achieved by regulating only the reaction temperature.…”

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confidence: 99%

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Tris(spiroborate)‐Type Anionic Nanocycles

Danjo

Mitani

Muraki

et al. 2012

Chemistry An Asian Journal

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Full circle: New cyclic tris(spiroborate)s were prepared as molecular recognition modules for nanometer-sized cationic guests. These cyclophanes were simply prepared by treating corresponding bis(2,3-dihydroxynaphthalene)s with an equimolar amount of boric acid. The molecular recognition ability of these cyclic spiroborates was estimated in solution and crystal phases by the use of [Ir(tpy(2))](3+) as a typical example of a cationic guest.

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Tetraanionic Organoborate Squares Glued Together by Cations To Generate Nanotubular Stacks

Cited by 18 publications

References 4 publications

An Iminoboronate Construction Set for Subcomponent Self‐Assembly

An Iminoboronate Construction Set for Subcomponent Self‐Assembly

Crystallization‐Controlled Dynamic Self‐Assembly and an On/Off Switch for Equilibration Using Boronic Ester Formation

Tris(spiroborate)‐Type Anionic Nanocycles

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