Design, synthesis and binding properties of conformer-independent linear ADA hydrogen-bonding arrays

Gooch, Adam; McGhee, Andrea M.; Renton, Lisa C.; Plante, Jeffrey; Lindsay, Christopher D.; Wilson, Andrew J.

doi:10.1080/10610270802468397

Cited by 18 publications

(21 citation statements)

References 29 publications

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“…It has been shown how hydrogen bonding can be used in designing the shape of aggregate [5][6][7] in solution and in solid state [8]. Generally, non-covalent intermolecular interactions are influenced by steric effects [9][10][11][12], electronic repulsion [11,13], position of the heteroatoms in the ring [14][15][16], and cooperative effects [17]. The atoms able to compete for hydrogen bonds (basic or acidic centers) are responsible for the conformational flexibility of NH-CO bond in amides [18][19][20].…”

Section: Introductionmentioning

confidence: 99%

The influence of CH bond polarization on the self-association of 2-acylaminopyrimidines by NH/CH···O/N interactions: XRD, NMR, DFT, and AIM study

et al. 2013

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The single crystal structures of two 2-acylaminopyrimidines, where alkyl groups in acyl moiety are iso-propyl (1) and dichloromethyl (2), were solved by X-ray diffraction method. The strength of intermolecular hydrogen bonding interactions depends on the C-H bond polarization increased by exchanging two methyl groups by chlorine atoms in the adjacent substituent. The computational methods provide an additional insight into the intermolecular interactions and are utilized in explaining the differences in the observed crystal structures. The experimental and computational data together explain the differences in the formed aggregates and revealed that these simple substitutions cause crucial changes in the intermolecular interactions.

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Section: Introductionmentioning

confidence: 99%

The influence of CH bond polarization on the self-association of 2-acylaminopyrimidines by NH/CH···O/N interactions: XRD, NMR, DFT, and AIM study

et al. 2013

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“…44 In a similar manner, we reasoned that exchange of the pyridine of the ureidopyridine motif for a pyrimidine would generate a conformer-independent ADA array and that such a motif may represent an alternative to thymine derivatives; we previously described triple hydrogen bonded heterocomplex PUPY·DAP 1 · 2 for which an association K a = 56 ± 20 M –1 was measured (Figure 1a). 45 We concluded that this moderate binding affinity was appropriate for side-chain supramolecular applications (Figure 1b), whereby several arrays may be incorporated into each macromonomer. This article describes incorporation of triple hydrogen bonding arrays based on model compounds 1 and 2 into monomer units of methyl methacrylate and styrene.…”

Section: Introductionmentioning

confidence: 92%

Side-Chain Supramolecular Polymers Employing Conformer Independent Triple Hydrogen Bonding Arrays

et al. 2013

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Derivatives of thymine have been extensively used to promote supramolecular materials assembly. Such derivatives can be synthetically challenging to access and may be susceptible to degradation. The current article uses a conformer-independent acceptor–donor–acceptor array (ureidopyrimidine) which forms moderate affinity interactions with diamidopyridine derivatives to effect supramolecular blend formation between polystyrene and poly(methyl methacrylate) polymers obtained by RAFT which have been functionalized with the hydrogen bonding motifs.

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“…[1][2][3][4][5] Not only do these systems represent excellent motifs to further our fundamental understanding of molecular recognition, but they also serve as building blocks for self-assembly [6][7][8] and biological probes. [9,10] In addition to the number of primary interactions, [11][12][13][14] the arrangement, [15,16] acidity/basicity of the hydrogen-bond donor/acceptors, [12,17,18] tautomerism, [19] electronic substituent effects [20,21] and conformation [22,23] all affect the affinity and specificity of the interactions made by linear arrays. Careful consideration of these factors should allow the design and development of motifs with high-fidelity recognition behaviour, [24] whilst using the minimum number of hydrogen bonds, which will potentially simplify synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…Much recent research has focused upon linear arrays employing four [12,13,[25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] or more [43][44][45][46][47] hydrogen bonds because of the enhanced strength of association that may be achieved. However, recent interest in triply hydrogen-bonded systems [15,[21][22][23][48][49][50][51][52] has illustrated that useful affinity can be achieved for assembly of dynamic architectures. [53][54][55][56] Within this family of hydrogen-bond receptors two classes emerge: I) rigid (poly)cyclic aromatic systems with pendant exocyclic hydrogen-bond donor/acceptor functionality [3,4] and II) systems in which individual donors (D) and acceptors (A) are separated from one another.…”

Section: Introductionmentioning

confidence: 99%

Conformer‐Independent Ureidoimidazole Motifs—Tools to Probe Conformational and Tautomeric Effects on the Molecular Recognition of Triply Hydrogen‐Bonded Heterodimers

Pellizzaro

McGhee

Renton

et al. 2011

Chemistry A European J

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Linear arrays of hydrogen bonds are useful for the reversible assembly of "stimuli-responsive" supramolecular materials. There is thus an ongoing requirement for easy-to-synthesise motifs that are capable of presenting hydrogen-bonding functionality in a predictable manner, such that high-affinity and high-fidelity recognition occurs. The design of linear arrays is made challenging as a consequence of their ability to adopt multiple conformational and tautomeric configurations; with each additional hydrogen-bonding heteroatom added to an array, the available tautomeric and conformational space increases and it can be difficult to anticipate where unproductive conformers/tautomers will arise. This paper describes a detailed study on the complementary ureidoimidazole donor-donor-acceptor (DDA) array (1) and amidoisocytosine donor-acceptor-acceptor (DAA) array (2). A specific feature of 1 is that two degenerate, intramolecular hydrogen-bonded conformations are postulated, both of which present a DDA array that is complementary to appropriate DAA partners. 1D and 2D (1)H NMR spectroscopy, isothermal titration calorimetry, and ab initio structure calculations confirm 1 interacts with 2 (K(a) ≈ 33,000 M(-1) in CDCl(3)) in a conformer-independent fashion driven by enthalpy. Comparison of the binding behaviour of 1 with hexylamidocytosine (4) and amidonaphthyridine (5) provides insight on the role that intramolecular hydrogen-bonding plays in mediating affinity towards DAA partners.

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Design, synthesis and binding properties of conformer-independent linear ADA hydrogen-bonding arrays

Cited by 18 publications

References 29 publications

The influence of CH bond polarization on the self-association of 2-acylaminopyrimidines by NH/CH···O/N interactions: XRD, NMR, DFT, and AIM study

The influence of CH bond polarization on the self-association of 2-acylaminopyrimidines by NH/CH···O/N interactions: XRD, NMR, DFT, and AIM study

Side-Chain Supramolecular Polymers Employing Conformer Independent Triple Hydrogen Bonding Arrays

Conformer‐Independent Ureidoimidazole Motifs—Tools to Probe Conformational and Tautomeric Effects on the Molecular Recognition of Triply Hydrogen‐Bonded Heterodimers

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