CHAPTER 4. A New Non-Covalent Bonding Mode in Supramolecular Chemistry: Main Group Element Lone-Pair–π(arene) Interactions

Caracelli, Ignez; Haiduc, Ionel; Zukerman-Schpector, Júlio; Tiekink, Edward R. T.

doi:10.1039/9781782626626-00098

Cited by 4 publications

(6 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Standard protocols were utilised to identify structures for the current survey [10]. The Cambridge Structural Database (CSD: version 5.37 + 2 updates) [14] was searched using CONQUEST (version 1.18) [15].…”

Section: Methodsmentioning

confidence: 99%

“…With the restriction that the element(lp)···π(arene) interaction operates in a given dimension within a crystal, in isolation from other supramolecular synthons, these interactions occur in a maximum of 14% of thallium(I) structures. This is reduced to 9% in bismuth(III) structures and down to a minimum of 2-3% for tin(II) and lead(II) compounds [9,10]. In terms of bonding, it is likely that the lone-pair···π interaction has similar features to halogen bonding [13] in that there is an asymmetric distribution of electron density in the lone-pair of electrons.…”

mentioning

confidence: 98%

“…main group element(lp)···π(arene), in the structural chemistry of main group element chemistry [2][3][4][5][6][7][8][9][10]. It is noted in passing that analogous interactions have been revealed in structural biology and are known to provide important stabilising contacts [11,12].…”

mentioning

confidence: 99%

“…It is noted in passing that analogous interactions have been revealed in structural biology and are known to provide important stabilising contacts [11,12]. In molecular structural chemistry, the emphasis thus far has been upon seeking "stand-alone" element(lp)···π(arene) contacts and determining the supramolecular architectures they sustain [2][3][4][5][6][7][8][9][10]. Usually these architectures are zero-and one-dimensional; however, examples of two-and even three-dimensional aggregation patterns are known [9,10].…”

mentioning

confidence: 99%

“…In molecular structural chemistry, the emphasis thus far has been upon seeking "stand-alone" element(lp)···π(arene) contacts and determining the supramolecular architectures they sustain [2][3][4][5][6][7][8][9][10]. Usually these architectures are zero-and one-dimensional; however, examples of two-and even three-dimensional aggregation patterns are known [9,10]. With the restriction that the element(lp)···π(arene) interaction operates in a given dimension within a crystal, in isolation from other supramolecular synthons, these interactions occur in a maximum of 14% of thallium(I) structures.…”

mentioning

confidence: 99%

See 4 more Smart Citations

14. Solute–solvent interactions mediated by main group element(lone-pair)···π(aryl) interactions

Tiekink¹,

Zukerman-Schpector²

2017

Multi-Component Crystals

Self Cite

View full text Add to dashboard Cite

Since the disclosure of tellurium(II, IV)···π(aryl) interactions in their crystal structures [1], there has been increasing interest in ascertaining the importance of this type of supramolecular synthon, i.e. main group element(lp)···π(arene), in the structural chemistry of main group element chemistry [2][3][4][5][6][7][8][9][10]. It is noted in passing that analogous interactions have been revealed in structural biology and are known to provide important stabilising contacts [11,12]. In molecular structural chemistry, the emphasis thus far has been upon seeking "stand-alone" element(lp)···π(arene) contacts and determining the supramolecular architectures they sustain [2][3][4][5][6][7][8][9][10]. Usually these architectures are zero-and one-dimensional; however, examples of two-and even three-dimensional aggregation patterns are known [9,10]. With the restriction that the element(lp)···π(arene) interaction operates in a given dimension within a crystal, in isolation from other supramolecular synthons, these interactions occur in a maximum of 14% of thallium(I) structures. This is reduced to 9% in bismuth(III) structures and down to a minimum of 2-3% for tin(II) and lead(II) compounds [9,10]. In terms of bonding, it is likely that the lone-pair···π interaction has similar features to halogen bonding [13] in that there is an asymmetric distribution of electron density in the lone-pair of electrons. This leaves an electropositive region at the tip of the lone-pair that interacts with the π electrons of the ring. This electron-deficient region is termed variously a σ-hole or polar cap, and the energy of stabilisation imparted by these interactions is in the region of 10 kJ mol −1 , i.e. similar to that imparted by C-H···π(aryl) interactions. In keeping with the theme of the present volume, "Aspects of Multi-Component Crystals: Synthesis, Concepts and Function", a description herein of the supramolecular architectures sustained by main group element(lp)···π(aryl) interactions is given where the π system is a solvent molecule such as benzene. ProceduresStandard protocols were utilised to identify structures for the current survey [10]. The Cambridge Structural Database (CSD: version 5.37 + 2 updates) [14] was searched using CONQUEST (version 1.18) [15]. There were two key geometric restraints, as illustrated in Figure 14.1a. The first restraint is the distance d, between the metal centre and the ring centroid, labelled Cg, which was set at 4.0 Å. This distance is shown to be suffihttps://doi

show abstract

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 98%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

14. Solute–solvent interactions mediated by main group element(lone-pair)···π(aryl) interactions

Tiekink¹,

Zukerman-Schpector²

2017

Multi-Component Crystals

Self Cite

View full text Add to dashboard Cite

show abstract

Host-guest interaction aided Zinc carry and delivery by ESIPT active 2-(2′-hydroxyphenyl)benzoxazole

Das

Brahma

Krishnamoorthy

2022

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

View full text Add to dashboard Cite

Sulfur(lone-pair)…π interactions with FAD in flavoenzymes

Silva

Sacco

Caracelli

et al. 2018

Zeitschrift Für Kristallographie - Crystalline Materials

View full text Add to dashboard Cite

The interactions of π-systems with lone-pairs of electrons are known and have been described in biological systems, involving lone-pairs derived from metals, metalloids, sulfur, oxygen and nitrogen. This study describes a bibliographic survey of the disulfide-bound sulfur(lone-pair) interactions with π-systems residing in the flavin adenine dinucleotide (FAD) cofactor of oxidoreductase enzymes (flavoenzymes). Thus, of the 172 oxidoreductase enzymes evaluated for gamma-S(lone-pair)…π(FAD) interactions, 96 proteins (56%) exhibited these interactions corresponding; 61% of 350 the constituent monomers featured at least one gamma-S(lone-pair)…π(FAD) interaction. Two main points of association between the S(lone-pair) and the isoalloxazine moiety of FAD were identified, namely at the centroid of the bond linking the uracil and pyrazine rings (60%), and the centroid of the uracil ring (37%). Reflecting the nature of the secondary structure in three prominent classes of oxidoreductase enzymes: glutathione disulfide reductases (GR; 21 proteins), trypanothione disulfide reductases (TR, 14) and sulfhydryl oxidases (SOX, 22), the approach of the gamma-S(lone-pair) to the FAD residue was to the si-face of the isoalloxazine ring system, i.e. to the opposite side as the carbonyl residue, for all GR and TR examples, and to the re-face for all SOX examples. Finally, the attractive nature of the gamma-S(lone-pair)…π(FAD) interactions was confirmed qualitatively by an examination of the non-covalent interaction plots.

show abstract

CHAPTER 4. A New Non-Covalent Bonding Mode in Supramolecular Chemistry: Main Group Element Lone-Pair–π(arene) Interactions

Cited by 4 publications

References 20 publications

14. Solute–solvent interactions mediated by main group element(lone-pair)···π(aryl) interactions

14. Solute–solvent interactions mediated by main group element(lone-pair)···π(aryl) interactions

Host-guest interaction aided Zinc carry and delivery by ESIPT active 2-(2′-hydroxyphenyl)benzoxazole

Sulfur(lone-pair)…π interactions with FAD in flavoenzymes

Contact Info

Product

Resources

About