Molecular Aggregation of Disklike Benzenetricarboxamides Containing Diacetylenic Groups in Bulk and Organic Solvents

Lee, Seung‐Ju; Park, Chong Rae; Chang, Ji Young

doi:10.1021/la0493417

Cited by 28 publications

(17 citation statements)

References 40 publications

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“…The concentration-independent value of the Cotton effect, the molar circular dichroism (De), was calculated as De = CD effect/A C H T U N G T R E N N U N G (32 980cl) in which c is the concentration in mol L À1 and l is the optical path length in cm. 1 H and 13 C NMR spectra were recorded on a Varian Gemini 400 MHz NMR spectrometer (400 MHz for 1 H NMR and 100 MHz for 13 C NMR). 1 H chemical shifts are reported in ppm downfield from tetramethylsilane (TMS) and 13 C chemical shifts are reported downfield from TMS with the resonance of the deuteriated solvent as the internal standard.…”

Section: Methodsmentioning

confidence: 99%

“…1 H and 13 C NMR spectra were recorded on a Varian Gemini 400 MHz NMR spectrometer (400 MHz for 1 H NMR and 100 MHz for 13 C NMR). 1 H chemical shifts are reported in ppm downfield from tetramethylsilane (TMS) and 13 C chemical shifts are reported downfield from TMS with the resonance of the deuteriated solvent as the internal standard. IR spectra were recorded on a Perkin-Elmer 1600 FT-IR spectrometer.…”

Section: Methodsmentioning

confidence: 99%

“…In recent years, we and others have explored in detail the properties of N,N',N''-trialkylbenzene-1,3,5-tricarboxamides (BTAs), discotic molecules consisting of a central benzene and three alkyl chains coupled to the core through amide bonds. [11] These simple compounds show considerable application potential as thermotropic liquid crystals, [12] organogels, [13] nucleating agents for isotactic polypropylene [14] and multivalent scaffolds for biomedical applications. [15] In addition, the effect of subtle changes in the molecular structures of BTAs on their self-assembling properties has been studied by our group.…”

Section: Introductionmentioning

confidence: 99%

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Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Mes

Cantekin

Balkenende

et al. 2013

Chemistry A European J

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The amide bond is a versatile functional group and its directional hydrogen-bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen-bonding-based self-assembling systems. We report herein the synthesis and characterisation of a new self-assembling motif comprising thioamides to induce directional hydrogen bonding. N,N',N''-Trialkylbenzene-1,3,5-tris(carbothioamide)s (thioBTAs) with either achiral or chiral side-chains have been readily obtained by treating their amide-based precursors with P2S5. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three-fold, intermolecular hydrogen-bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self-assemble into one-dimensional, helical supramolecular polymers stabilised by three-fold hydrogen bonding. Concentration- and temperature-dependent self-assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D(trans) and D(rot), were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L = 490 nm and d = 3.6 nm). These measured values are in good agreement with the value L(w) = 755 nm obtained from fitting the temperature-dependent CD data by using a recently developed equilibrium model. This experimental verification validates our common practice for determining the length of BTA-based supramolecular polymers from model fits to experimental CD data. The ability of thioamides to induce cooperative supramolecular polymerisation makes them effective and broadly applicable in supramolecular chemistry.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Mes

Cantekin

Balkenende

et al. 2013

Chemistry A European J

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“…[4′‐(4‐Acetylphenyl)phenylethynyl]‐4‐dodecyloxybenzene (3): 4‐Iodo(dodecyloxy)benzene22 (280 mg, 0.5 mmol) and 1 (165 mg, 0.75 mmol) were treated and purified under the same conditions as for 2 to give pure 3 as pale yellow solid after final recrystallization from EtOH in 67 % yield (161 mg). 1 H NMR (300 MHz, CDCl 3 ): δ = 8.04 (d AB , J = 8.2 Hz, 2 H), 7.70 (d AB , J = 8.2 Hz, 2 H), 7.60 (s, 4 H), 7.48 (d AB , J = 8.8 Hz, 2 H), 6.88 (d AB , J = 8.8 Hz, 2 H), 3.98 (t, J = 6.5 Hz, 2 H), 2.64 (s, 3 H), 1.79 (q, J = 5.5 Hz, 2 H), 1.48–1.27 (m, 18 H) 0.88 (t, J = 6.8 Hz, 3 H) ppm.…”

Section: Methodsmentioning

confidence: 99%

Biphenyl‐Based Disc‐ vs. Rod‐Shaped Phenylacetylenes: Mesomorphism and Electronic Properties

Hennrich¹,

Ortíz²,

Cavero³

et al. 2008

Eur J Org Chem

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A standard Sonogashira coupling protocol has been applied for the preparation of a C 3 -symmetric phenylacetylene (2) and the corresponding linear phenylacetylene (3) incorporating terminal biphenyl substituents. The study of the mesomorphic properties of the target compounds, as well as mixtures of both, reveals that only the calamitic biphenylylacetylene 3 forms smectic liquid crystals. Upon investigating the

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“…In particular, controlling the morphology of crystalline materials is of vital importance for pharmaceutical applications due to the bioavailability of drugs as well as for organic semiconductors with respect to the performance and function of thin film devices . Besides, supramolecular nanofibers are expected to have a great potential and to see use as organo and hydrogelators, polymer additives such as nucleating and clarifying agent, and fibrous materials for filtration applications . Typically, these self‐assembly systems are based on the formation of reversible noncovalent interactions such as hydrogen bonds, π–π‐stacking, or metal–ligand coordination.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Alkoxy-Substituted 1,3,5-Benzenetrisamides Under Controlled Conditions

Weiß

Kreger

Schmidt

2016

Macromol. Mater. Eng.

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polymer additives such as nucleating and clarifying agent, [19][20][21][22][23][24][25][26] and fibrous materials for filtration applications. [27,28] Typically, these self-assembly systems are based on the formation of reversible noncovalent interactions such as hydrogen bonds, π-π-stacking, or metal-ligand coordination. Apart from the plethora of literature-known supramolecular motifs, a variety of studies have been reported on 1,3,5-benzenetrisamides (BTAs) as a simple structural motif. [13,29,30] These materials are designed to form supramolecular columns by directed threefold hydrogen bonding of the amide moieties between the individual building blocks. [31][32][33][34] The self-assembly of BTAs from solution yielding supramolecular nanofibers is governed by a variety of different parameters such as the molecular structure of the BTA, the selected solvent system, the concentration, and the applied temperature protocol during processing. The self-assembly process from solutions of BTAs to nanofibers can be initiated by changes of solvent quality, evaporation of the solvent, or temperature changes. For instance, one method to induce the selfassembly of BTAs is the addition of a nonsolvent to a BTA Supramolecular nanofibers have a great potential to be used as gelating agents, polymer additives, and fibrous material for filtration purposes. To meet the requirements for practical and industrial applications on a large scale, e.g., production of filter media, it is desirable to develop supramolecular systems processable from environmentally friendly water-based solvent mixtures. Moreover, assessing processing parameters to control the micro-and nanofiber diameter is of vital importance. Therefore, an alkoxy-substituted 1, 3,5-benzenetrisamide, N,N′,N″-tris(1-(methoxymethyl)propyl)benzene-1,3,5-tricarboxamide is designed that can be self-assembled into supramolecular nanofibers upon cooling from a water/isopropanol solvent mixture. It is demonstrated that parameters such as stirring velocity and the temperature range during processing allow for a precise adjustment of the cooling profile which in turn enables the control of the supramolecular nanofiber diameters.

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Molecular Aggregation of Disklike Benzenetricarboxamides Containing Diacetylenic Groups in Bulk and Organic Solvents

Cited by 28 publications

References 40 publications

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Biphenyl‐Based Disc‐ vs. Rod‐Shaped Phenylacetylenes: Mesomorphism and Electronic Properties

Self-Assembly of Alkoxy-Substituted 1,3,5-Benzenetrisamides Under Controlled Conditions

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