Synthesis and noncovalent polymerization of self-complementary hydrogen-bonding supramolecular synthons: N,N′-disubstituted 4,6-diamino-pyrimidin-2(1H)-ones

Yagai, Shiki; Iwashima, Tomoyuki; Karatsu, Takashi; Kitamura, Akihiro

doi:10.1039/b401132e

Cited by 30 publications

(16 citation statements)

References 14 publications

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“…5 As a result, the reduction in chain length is very efficient, even in the presence of small amounts of chain-stopper. 5−10 The impact of chain-stoppers on the decrease of the molecular weights of the isodesmic supramolecular polymers and on their property changes have been studied in great detail. 11…”

Section: Introductionmentioning

confidence: 99%

Tuning the Length of Cooperative Supramolecular Polymers under Thermodynamic Control

Vantomme¹,

Huurne²,

Kulkarni³

et al. 2019

J. Am. Chem. Soc.

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In the field of supramolecular (co)polymerizations, the ability to predict and control the composition and length of the supramolecular (co)polymers is a topic of great interest. In this work, we elucidate the mechanism that controls the polymer length in a two-component cooperative supramolecular polymerization and unveil the role of the second component in the system. We focus on the supramolecular copolymerization between two derivatives of benzene-1,3,5-tricarboxamide (BTA) monomers: a-BTA and Nle-BTA. As a single component, a-BTA cooperatively polymerizes into long supramolecular polymers, whereas Nle-BTA only forms dimers. By mixing a-BTA and Nle-BTA in different ratios, two-component systems are obtained, which are analyzed in-depth by combining spectroscopy and light-scattering techniques with theoretical modeling. The results show that the length of the supramolecular polymers formed by a-BTA is controlled by competitive sequestration of a-BTA monomers by Nle-BTA, while the obvious alternative Nle-BTA acts as a chain-capper is not operative. This sequestration of a-BTA leads to short, stable species coexisting with long cooperative aggregates. The analysis of the experimental data by theoretical modeling elucidates the thermodynamic parameters of the copolymerization, the distributions of the various species, and the composition and length of the supramolecular polymers at various mixing ratios of a-BTA and Nle-BTA. Moreover, the model was used to generalize our results and to predict the impact of adding a chain-capper or a competitor on the length of the cooperative supramolecular polymers under thermodynamic control. Overall, this work unveils comprehensive guidelines to master the nature of supramolecular (co)polymers and brings the field one step closer to applications.

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Section: Introductionmentioning

confidence: 99%

Tuning the Length of Cooperative Supramolecular Polymers under Thermodynamic Control

Vantomme¹,

Huurne²,

Kulkarni³

et al. 2019

J. Am. Chem. Soc.

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“…The discussion has been restricted to a few systems on chain stoppered supramolecular polymers. More examples have been reported in the self-assembly of calixarenes, 163,164 , polypseudorotaxanes, 165,166 self-assembling N,N 0 -disubstituted diamino-pyrimidinones, 167 ureidotriazines, 168 cucurbit [8]uril-and iron coordination based supramolecular polymers, 169 cyanuric wedge-isopthalamide receptor arrays, 170 and rodlike self-assembled bimetallic tetracarboxylates.…”

mentioning

confidence: 99%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

128

102

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The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

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“…[12] Column chromatography was performed on 63-210 mm silica gel. The solvents for the spectroscopic measurements and the gelling experiments were all spectral grade and were used without further purification.…”

Section: Methodsmentioning

confidence: 99%

“…We recently reported the synthesis and the self-as- Figure 1) featuring donor-donor-acceptor (DDA) and acceptor-acceptor-donor (AAD) hydrogenbonding arrays. [12] These selfcomplementary guanine-cytosine hybridized supramolecular building blocks are based on 5-octyl-4,6-diaminopyrimidin-2-A C H T U N G T R E N N U N G (1 H)-one, reported by Lehn et al in 1992, [13] but they can be functionalized even more easily. DAP building blocks possessing long aliphatic chains have been shown to form robust supramolecular tapes in solution and in the solid state, so a lot of functionalized supramolecular tapes based on DAP building blocks are available.…”

Section: Introductionmentioning

confidence: 99%

Photoresponsive Self‐Assembly and Self‐Organization of Hydrogen‐Bonded Supramolecular Tapes

Yagai

Iwashima

Kishikawa

et al. 2006

Chemistry A European J

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Self-assembling building blocks that are readily functionalizable and capable of achieving programmed hierarchical organization have enabled us to create various functional nanomaterials. We have previously demonstrated that N,N'-disubstituted 4,6-diaminopyrimidin-2(1 H)-one (DAP), a guanine-cytosine hybridized molecule, is a versatile building block for the creation of tapelike supramolecular polymer species in solution. In the current study, DAP was functionalized with azobenzene side chains. 1H NMR, UV/Vis, and dynamic light scattering studies confirmed the presence of nanometer-scale tapelike supramolecular polymers in alkane solvents at micromolar regimes. At higher concentrations (millimolar regimes), the supramolecular polymers hierarchically organized into lamellar superstructures to form organogels, as shown by X-ray diffraction and polarized optical microscopy. Remarkably, the azobenzene side chains are photoisomerizable even in the supramolecular polymers, owing to their loosely packed state supported by the rigid hydrogen-bonded scaffold, enabling us to establish photocontrollable supramolecular polymerization and higher order organization of the tapelike supramolecular polymers into lamellar superstructures.

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Synthesis and noncovalent polymerization of self-complementary hydrogen-bonding supramolecular synthons: N,N′-disubstituted 4,6-diamino-pyrimidin-2(1H)-ones

Cited by 30 publications

References 14 publications

Tuning the Length of Cooperative Supramolecular Polymers under Thermodynamic Control

Tuning the Length of Cooperative Supramolecular Polymers under Thermodynamic Control

Controlling supramolecular polymerization through multicomponent self‐assembly

Photoresponsive Self‐Assembly and Self‐Organization of Hydrogen‐Bonded Supramolecular Tapes

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