Structural characterization, recognition patterns and theoretical calculations of long-chain N-alkyl substituted purine and pyrimidine bases as ligands: On the importance of anion–π interactions

Fiol, Juan J.; Barceló‐Oliver, Miquel; Tasada, Andrés; Frontera, Antonio; Terrón, Àngel; Garcı́a-Raso, Ángel

doi:10.1016/j.ccr.2012.12.013

Cited by 43 publications

(21 citation statements)

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“…Both experimental and theoretical evidence of interesting synergetic effects between anion-π and HB and between anion-π and π−π stacking interactions has been reported recently which displays that the interplay between these interactions can direct to strong cooperativity effects. [29][30][31][32][33][34][35][36][37][38][39][40] Recently, experimental evidence of anion-π-π interactions has emerged from crystallographic studies [41][42][43][44] on synthesized compounds based on the electron-deficient pyridine moieties, suggesting the possibility to enhance anion-π binding by π-π stacking. In the present study, we investigate and explore the structural features of this anion-π-π complex, and the energetic associated to anion-π, π + -π + and π + -π interactions using a combination of single crystal X-ray diffraction and density 3 functional theory (DFT) calculations.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Study of Counterintuitive ClO₄^–···ClO₄^– Interactions and the Interplay between π⁺–π and Anion···π⁺ Interactions

Manna

Seth²,

Mitra

et al. 2014

Crystal Growth & Design

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115

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The novel non-covalent interactions between the charged and neutral aromatic rings and with anions are utilized to design the solid-state assembly of triply protonated PTPH 3 (PTP = 4'-(4-pyridyl)-3,2':6',3''-terpyridine) with H 2 O and three ClO 4 -, which is synthesized and characterized by single crystal X-ray diffraction analysis. Crystallography reveals that the π + -π + , π + -π and various anion···π interactions are the major driving forces in the stabilization of the selfassembled structure. In the title complex, a layered assembly is formed through the mutual influence of π + -π + and π + -π interactions. The anions are interacting with the charged π-acceptors which are again stabilized through π + -π interactions. So, the overall stabilization is governed through π + -π/π-π + , (π + -π + ) n and anion···π + /π + -π/π-π + networks in the solid state. The interaction energies of the main driving forces observed in the crystal structure have been calculated using density functional theory. In addition, the short O···O contact between ClO 4 -, anions has been analyzed in detail both computationally and exploring the Cambridge Structural Database.

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Section: Introductionmentioning

confidence: 99%

Experimental and Computational Study of Counterintuitive ClO₄^–···ClO₄^– Interactions and the Interplay between π⁺–π and Anion···π⁺ Interactions

Manna

Seth²,

Mitra

et al. 2014

Crystal Growth & Design

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115

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“…The geometric and energetic features of anion-π + complexes of several aromatic cations (tropylium, quinolizinylium) and various anions have been reported along with crystallographic structures [87,88]. This field of research has recently attracted attention and several works have appeared in the literature [89,91]. For instance, the anion-π + interaction participates in the formation of a robust recognition motif in the transition metal malonate complexes using protonated 2-amino-4-picoline and 2-aminopyridine as the auxiliary ligands [89,90].…”

Section: Physical Naturementioning

confidence: 98%

“…Distances in Å due to strong electrostatic effects that dominate the interaction. The anion-π + interaction in protonated purine and pyrimidine bases has been recently reviewed [91] demonstrating the importance of this interaction in biologically relevant compounds.…”

Section: Physical Naturementioning

confidence: 99%

Anion-π Interactions in Supramolecular Chemistry and Catalysis

Bauzá

Deyà

Frontera

2015

Challenges and Advances in Computational Chemistry and Physics

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Non-covalent interactions play a major role in supramolecular chemistry and biochemistry by dominating the central parts of living systems since they dictate the functionality of many biological and host-guest systems. A good comprehension of the different non-covalent forces is necessary for the rational design of new drugs and developing improved synthetic receptors capable to function in competitive media. Interactions involving aromatic rings (or π-systems in general) are very relevant in supramolecular chemistry, exemplified by the cation-π interaction and its importance in protein structure and enzyme catalysis. From a traditional point of view, the π-system is usually considered as electron rich (π-basic). The naissance of the counterintuitive anion-π interaction -the attractive interaction between an anion and an electron poor π-system (π-acid)-was somewhat controversially discussed by the scientific community. However, in the last decade a great deal of theoretical and experimental investigations has time-honored the anion-π interaction as an important supramolecular bond. Herein we describe the physical nature of this noncovalent interaction and the different strategies that can be used to modulate its strength. Finally, selected state-of-the-art reports illustrating the rational utilization of the anion-π interaction in supramolecular chemistry (anion receptors), biological applications and catalysis are described in this chapter.

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“…Moreover, the electronic nature of the other ligands coordinated to the metal also influences the interaction strength [20,53]. Lastly, the importance of this inter action in protonated purine and pyrimidine bases has been recently reviewed [84]. For example, pyridine and related azines can be easily protonated by adjusting the pH of the medium, thus increasing the anion binding ability of the ring (anion-π + interactions).…”

Section: Physical Naturementioning

confidence: 99%

Construction of Supramolecular Assemblies Based on Anion–π Interactions

Bauzá

2016

Non‐covalent Interactions in the Synthesis and Design of New Compounds

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Structural characterization, recognition patterns and theoretical calculations of long-chain N-alkyl substituted purine and pyrimidine bases as ligands: On the importance of anion–π interactions

Cited by 43 publications

References 58 publications

Experimental and Computational Study of Counterintuitive ClO₄^–···ClO₄^– Interactions and the Interplay between π⁺–π and Anion···π⁺ Interactions

Experimental and Computational Study of Counterintuitive ClO₄^–···ClO₄^– Interactions and the Interplay between π⁺–π and Anion···π⁺ Interactions

Anion-π Interactions in Supramolecular Chemistry and Catalysis

Construction of Supramolecular Assemblies Based on Anion–π Interactions

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Structural characterization, recognition patterns and theoretical calculations of long-chain N-alkyl substituted purine and pyrimidine bases as ligands: On the importance of anion–π interactions

Cited by 43 publications

References 58 publications

Experimental and Computational Study of Counterintuitive ClO4–···ClO4– Interactions and the Interplay between π+–π and Anion···π+ Interactions

Experimental and Computational Study of Counterintuitive ClO4–···ClO4– Interactions and the Interplay between π+–π and Anion···π+ Interactions

Anion-π Interactions in Supramolecular Chemistry and Catalysis

Construction of Supramolecular Assemblies Based on Anion–π Interactions

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Experimental and Computational Study of Counterintuitive ClO₄^–···ClO₄^– Interactions and the Interplay between π⁺–π and Anion···π⁺ Interactions

Experimental and Computational Study of Counterintuitive ClO₄^–···ClO₄^– Interactions and the Interplay between π⁺–π and Anion···π⁺ Interactions