Preparation of layered diacetylenes as a demonstration of strategies for supramolecular synthesis.

Kane, John; Liao, Ruey-Fen; Lauher, Joseph W.; Fowler, Frank W.

doi:10.1021/ja00153a026

Cited by 153 publications

(110 citation statements)

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“…For most examples, this interaction relies on hydrogen-bonding, which is a directionalreversible interaction with adjustable binding strength (4, 5). Within the family of hydrogen-bonded systems, the association of carboxylic acids and pyridines has received special attention and includes work on defined molecular assemblies (6-9), supramolecular polymers and networks (4,5,(10)(11)(12)(13)(14), and hydrogen-bonded liquid crystals (15-18). However, the lowbinding constant between pyridines and carboxylic acids precludes high degrees of polymerization in solution between dicarboxylic acid and dipyridine building blocks, which, up to now, limited this supramolecular synthon to applications in solid-state materials.…”

mentioning

confidence: 99%

Hydrogen bond-directed aggregation of diazadibenzoperylene dyes in low-polarity solvents and the solid state

Sautter

Thalacker²,

Heise³

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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The formation of complex superstructures via hydrogen bonding of two ditopic building blocks, diazadibenzoperylenes 1a,b and isophthalic acid 2, has been investigated. It was found that only the phenoxy-substituted diazadibenzoperylene 1a forms extended assemblies with 2 in complexes of a 1:1 stoichiometry, whereas for the 4-tert-butylphenoxy-substituted analogue 1b, no indications for superstructure formation with 2 were found. The different behavior is explained by the presence of additional -interactions, which are only observed for [1a⅐2], as revealed by concentration-dependent optical absorption and fluorescence spectroscopy. Based on variable temperature x-ray diffraction studies, a lamellar structure for [1a⅐2] is proposed that takes into account the concept of microphase-segregation.T he current demand in highly ordered solid-state -conjugated materials for application in electronic devices, e.g., organic field-effect transistors and organic solar cells (1-3), constitutes a touchstone for supramolecular chemistry that stimulates several groups to synthesize receptor-functionalized chromophores and to control their solid-state organization by means of intermolecular forces (1-5). For most examples, this interaction relies on hydrogen-bonding, which is a directionalreversible interaction with adjustable binding strength (4, 5). Within the family of hydrogen-bonded systems, the association of carboxylic acids and pyridines has received special attention and includes work on defined molecular assemblies (6-9), supramolecular polymers and networks (4,5,(10)(11)(12)(13)(14), and hydrogen-bonded liquid crystals (15-18). However, the lowbinding constant between pyridines and carboxylic acids precludes high degrees of polymerization in solution between dicarboxylic acid and dipyridine building blocks, which, up to now, limited this supramolecular synthon to applications in solid-state materials. Nevertheless, as shown recently, the binding constants of hydrogen bonds increase considerably with decreasing competition of the solvent with the receptor groups, which is given, for example, in aliphatic solvents (5). If additional weaker interactions such as -interactions or microphasesegregation (19,20) favorably contribute to the self-assembly process, then a hierarchical superstructure formation becomes likely in the solid state or even in dilute solution.In the given contribution, highly fluorescent diazadibenzoperylene dyes 1a,b (21) were chosen as a ditopic hydrogen-bond acceptor, and their interaction with ditopic hydrogen-bond donating isophthalic acid 2 (22) § was studied in solution and the solid state (Fig. 1). A prerequisite for the formation of extended hydrogen-bonded polymers is an exact 1:1 stoichiometry between the precursors 1a,b and 2. Special care had to be taken in the preparation of the complexes, because even the slightest deviation from the exact stoichiometry results in low degrees of polymerization and will shift the equilibria toward short oligomers (5). Already in the course of preparing the...

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mentioning

confidence: 99%

Hydrogen bond-directed aggregation of diazadibenzoperylene dyes in low-polarity solvents and the solid state

Sautter

Thalacker²,

Heise³

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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“…Generally, the signal intensity of the NMR spin-echo depends on the relaxation times T 1 , T 2 as well as on ρ and τ [11,14,15]. In our case the images shown in Fig.…”

Section: Resultsmentioning

confidence: 65%

“…The compound studied, toluene-based bis-urea, is an organogelator where the bifurcated hydrogen bonds between urea groups are responsible for the molecular self-assembling [9][10][11]. Usually the procedure for a gel formation consists of heating of the mixture of low-molecular weight gelator and a solvent in closed tube to promote homogeneity of the system, and next cooling up to trap solvent molecules in the assembled entangled network.…”

Section: Introductionmentioning

confidence: 99%

Gelation Process of Toluene-Based bis-Urea in Cyclohexane Studied with Magnetic Resonance Imaging

et al. 2005

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Magnetic resonance imaging was used for studies of the gelation and swelling processes of toluene-based bis-urea prepared in a form of cylindrical tablet and immersed in cyclohexane. The processes were investigated with the use of Bruker AVANCE (300 MHz) spectrometer equipped with a micro imaging probe head. The images were taken for cyclohexane protons within the bis-urea gel formed around the sample dry core at different intervals of the immersion. The mobility of the solvent molecules was estimated from the spatially resolved distribution of the spin-spin relaxation time T2 and the spin densities ρ, calculated on the basis of the images obtained. It was shown that the time-evolution of the thickness of the gel layer can be well described by the power equation with an exponent equal to 0.47 (±0.04), indicating the Fickian nature of the diffusion of cyclohexane molecules.

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“…However, these claims are severely questionable. They were only made on the basis of color changes and only in a footnote [140] without any proof for trans-tactic polymerization (there might at best have been phase transitions or uncontrolled reactions whatsoever). This was nevertheless quoted and compared to a different cocrystal with a so-called equally suitable spacing of 4.97 Å in a short review as if it were the same as with the clearly unreactive 4.71 and 4.63 distances [141].…”

Section: Linear Polymerizationsmentioning

confidence: 99%

Organic Solid-State Reactions

Kaupp

2016

Encyclopedia of Physical Organic Chemistry, 5 Volume Set

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Preparation of layered diacetylenes as a demonstration of strategies for supramolecular synthesis.

Cited by 153 publications

References 0 publications

Hydrogen bond-directed aggregation of diazadibenzoperylene dyes in low-polarity solvents and the solid state

Hydrogen bond-directed aggregation of diazadibenzoperylene dyes in low-polarity solvents and the solid state

Gelation Process of Toluene-Based bis-Urea in Cyclohexane Studied with Magnetic Resonance Imaging

Organic Solid-State Reactions

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