Enhanced Small-Molecule Assembly through Directional Intramolecular Forces

Lampkins, Andrew J.; Abdul-Rahim, Osama; Li, Hengfeng; Castellano, Ronald K.

doi:10.1021/ol051768x

Cited by 24 publications

(32 citation statements)

References 33 publications

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“…SEM analysis, for example, reveals that fibrous morphologies emerge upon drop-casting a solution of 2 on a glass slide [37]. Moreover, the experimental XRD data reveals an intracolumnar core-to-core distance of 5.2 Å, consistent with the spacings predicted here [10]. Less conclusive is whether intermolecular hydrogen bonding plays a role in the experimentally observed assembly of 2.…”

Section: Assembly Ofsupporting

confidence: 71%

“…For 1, NOESY (NMR) experiments in solution have verified the close spatial relationship of the peripheral phenyl groups to the core (NOEs are observed between the aromatic protons and N-␣-CH 2 protons) [9]. For 2, both solution-phase and solid-state NMR studies have revealed the intramolecular hydrogen bonding shown (vide infra) and demonstrated the predicted C 3 -symmetry of the molecule [10].…”

Section: Monomer Structuresmentioning

confidence: 81%

“…The lowest energy conformation for each of two recently synthesized molecules, AATs 1 and 2 [9,10], are shown in Figure 1. Both molecules are C 3 -symmetric and propeller-shaped.…”

Section: Monomer Structuresmentioning

confidence: 99%

“…To this end, we have explored the self-assembly of triamide AAT 2, a second compound that was recently synthesized [10]. Geometry optimizations of the homochiral dimeric structure [ Fig.…”

Section: Assembly Ofmentioning

confidence: 99%

“…Recently, the first functionalized donor--acceptor molecules based on 1-aza-adamantanetriones (AATs) were synthesized [9,10]. These functionalized AAT molecules ( Fig.…”

mentioning

confidence: 99%

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Investigation of the nanoscale self‐assembly of donor‐σ‐acceptor molecules

Sumpter

Meunier

Vázquez‐Mayagoitia

et al. 2007

Int J of Quantum Chemistry

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Electronic structure calculations are used to explore the nature of the interactions that lead to the self-assembly of a new class of functionalized donor--acceptor molecules, 1-aza-adamantanetriones (AATs), and the consequences of molecular structure on the resulting supramolecular systems. The results show how the self-assembly process originates from the saturated core of the molecules that underlies their shape, conformational preferences, and dipole-directed one-dimensional assembly. The solvation properties of the monomers are explored and 1 H NMR chemical shift values are determined and compared to experimental trends. A theoretical understanding of this class of supramolecular structures coupled with their molecularlevel tunability introduces the possibility to design novel functional materials for specific electronic and optoelectronic applications.

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Section: Assembly Ofsupporting

confidence: 71%

Section: Monomer Structuresmentioning

confidence: 81%

“…The lowest energy conformation for each of two recently synthesized molecules, AATs 1 and 2 [9,10], are shown in Figure 1. Both molecules are C 3 -symmetric and propeller-shaped.…”

Section: Monomer Structuresmentioning

confidence: 99%

“…To this end, we have explored the self-assembly of triamide AAT 2, a second compound that was recently synthesized [10]. Geometry optimizations of the homochiral dimeric structure [ Fig.…”

Section: Assembly Ofmentioning

confidence: 99%

“…Recently, the first functionalized donor--acceptor molecules based on 1-aza-adamantanetriones (AATs) were synthesized [9,10]. These functionalized AAT molecules ( Fig.…”

mentioning

confidence: 99%

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Investigation of the nanoscale self‐assembly of donor‐σ‐acceptor molecules

Sumpter

Meunier

Vázquez‐Mayagoitia

et al. 2007

Int J of Quantum Chemistry

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Assessable Consequences of Through‐Bond Donor–Acceptor Interactions in β‐Aminoketones

Lampkins

Abbas

et al. 2008

Chemistry A European J

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Reported are the syntheses of ester-functionalized (6-8) and alkyl-substituted (9) 1-aza-adamantanones; the easy handling of the compounds provides an opportunity to comprehensively study the fundamental changes in structure and reactivity that can accompany the donor-acceptor arrangement in rigid beta-aminoketones. X-ray structural analysis of trione 6 and dione 7 reveals bond length and angle variations consistent with through-bond (hyperconjugative) donor-acceptor interactions. Observed is a shortening of the C-N bond, elongation of the central C-C bond (to approximately 1.6 A), and a significant pyramidalization of the carbonyl carbon within the donor-sigma-acceptor pathway. UV/Vis spectra of 6-9 show a new absorption maximum (lambda(max)=260-275 nm in three solvents), the so-called "sigma-coupled transition"; the molar absorptivity scales with the number of carbonyl groups (for trione 6, epsilon approximately 3000, for dione 7, epsilon approximately 2000) and the band reversibly disappears upon addition of acid. IR and (13)C NMR spectroscopic data show trends consistent with through-bond donation to the carbonyl acceptor groups and commensurate weakening of the carbonyl pi bond. High yielding acid-mediated fragmentations are used to illustrate the effects of the donor-acceptor arrangement on the reactivity of the molecules. Given that donor-sigma-acceptor molecules have recently been found to show self-assembly behavior and macromolecular properties linked to their unusual structure, the current analysis encourages further consideration of the systems in advanced materials applications.

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Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

Castellano

Homan

et al. 2012

Eur J Org Chem

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Seven‐membered intramolecular hydrogen bonding (7MHB) arrangements involving phenolic hydroxyl group donors have been investigated through Cambridge Structural Database (CSD) and literature mining, and by the characterization of model compounds. The CSD reveals the numerous H‐bond accepting functional groups that can participate in 7MHB when they are proximal to a phenolic OH, including alcohols, amides, amines, ethers, N‐containing heterocycles, ketones, N‐oxides, phosphates, and phosphane oxides. The HB contacts are defined by Ophenol···N and Ophenol···O distances of ca. 2.7 Å, and two dihedral angles that fall within the range of typical peptide γ‐turns. Two of the identified 7MHB motifs have been readily mapped onto the phloroglucinol (1,3,5‐trihydroxybenzene) scaffold to provide eight model compounds; intramolecular hydrogen bonding involving all three hydroxyl groups is shown to persist in solution and the solid state for the compounds. Intramolecular 7MHB enforces nonplanar conformations that should be useful when designing molecular hosts and catalysts.

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Enhanced Small-Molecule Assembly through Directional Intramolecular Forces

Cited by 24 publications

References 33 publications

Investigation of the nanoscale self‐assembly of donor‐σ‐acceptor molecules

Investigation of the nanoscale self‐assembly of donor‐σ‐acceptor molecules

Assessable Consequences of Through‐Bond Donor–Acceptor Interactions in β‐Aminoketones

Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

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