Aromaticity and Chemical Bonding of Chalcogen‐Bonded Capsules Featuring Enhanced Magnetic Anisotropy

Abstract

We present a theoretical study of chalcogen bonded container capsules (A X + A X) where X=O, S, Se, and Te, and their encapsulation complexes with n-C 9 H 20 (n-C 9 H 20 @A X + A X). Both Se and Te encapsulation complexes have significant experimental and computed binding energies, analogous to the hydrogen bonded counterparts, while the S and O capsules and their encapsulation complexes show only weak binding energies, which are attributed to different types of bonding: chalcogen S•••N bonds for S-capsules and π-π stacking and weak hydrogen bonds for the O case. All A X + A X and C 9 H 20 @A X + A X present unusually high magnetic anisotropies in their interiors. The 1 H NMR spectra of the encapsulation complexes display the proton signals of the encapsulated n-nonane highly upfield shifted, in agreement with the available experimental data for the Se capsule. We found that different factors contribute to the observed magnetic anisotropy of the capsule's interior: for the Te capsule the most important factor is Te's large polarizability; for the O analogue the inductive effects produced by the electronegative nature of the O and N heteroatoms; and for the S and Se capsules, the polarizability of the heteroatoms combines with electric field effects.

Optimizing the self‐assembly of conjugated polymers and small molecules through structurally programmed non‐covalent control

“…These findings were elaborated in a computational study by Tzeli et al, also in 2020. 170 Calculations of the binding energies of dimeric complexes consisting of cavitands with four chalcogen atoms (O, S, Te, Se) revealed stronger binding energies in Se and Te cavitands than S and O, as well as more effective encapsulation of n-nonane.…”

Chalcogen-bonded donor–acceptor complexes of 5,6-dicyano[1,2,5]selenadiazolo[3,4-b]pyrazine with halide ions

“…Currently, such interactions/bondings attract enhanced interest due to their generality and potential applications, e.g. in anion recognition [28][29][30][31][32][33][34] and transport, 35,36 organocatalysis, [37][38][39] supramolecular chemistry and crystal engineering, [40][41][42] and materials chemistry. 43 With chalcogen bonding, the compounds under discussion in the homocrystals are often connected by [E-N] 2 square supramolecular synthons (E = S, Se, Te).…”

“…Currently, such interactions/bondings attract enhanced interest due to their generality and potential applications, e.g. in anion recognition 28–34 and transport, 35,36 organocatalysis, 37–39 supramolecular chemistry and crystal engineering, 40–42 and materials chemistry. 43…”

Charge Assisted S/Se Chalcogen Bonds in SAM Riboswitches: A Combined PDB and ab Initio Study

“… 3 Despite the great importance that hydrogen bonding interactions (HB) play in many chemical and biological systems, 4 , 5 such as in enzymatic chemistry and protein folding and binding phenomena, 6 other noncovalent interactions based on the p-block of elements (aerogen, 7 halogen, 8 chalcogen, 9 pnictogen, 10 and tetrel bonds) 11 have emerged as novel and powerful resources for rational drug design, 12 − 14 molecular aggregation 15 − 17 or even tuning self-assembly processes. 18 − 20 Among them, chalcogen bonds (ChBs) have been studied both theoretically 21 − 24 and experimentally in several areas of research, such as host–guest chemistry, 25 , 26 crystal engineering and materials science, 27 − 29 and catalysis. 30 , 31 In biology, ChBs have been mainly studied in protein–ligand complexes, 32 involving glucosidases, 33 Zn finger proteins, 34 C-Jun N-terminal kinase 3, 35 iodothyronine deiodinase, 36 and lysine methyltransferase SET7/9 37 systems.…”

“…During the past decade, noncovalent interactions (NCIs) have started a fast growing revolution, which has led them to become essential resources of the chemist toolbox owing to their crucial role in several fields of modern chemistry, such as supramolecular chemistry, molecular recognition, and materials science . Despite the great importance that hydrogen bonding interactions (HB) play in many chemical and biological systems, , such as in enzymatic chemistry and protein folding and binding phenomena, other noncovalent interactions based on the p-block of elements (aerogen, halogen, chalcogen, pnictogen, and tetrel bonds) have emerged as novel and powerful resources for rational drug design, − molecular aggregation − or even tuning self-assembly processes. − Among them, chalcogen bonds (ChBs) have been studied both theoretically − and experimentally in several areas of research, such as host–guest chemistry, , crystal engineering and materials science, − and catalysis. , In biology, ChBs have been mainly studied in protein–ligand complexes, involving glucosidases, Zn finger proteins, C-Jun N-terminal kinase 3, iodothyronine deiodinase, and lysine methyltransferase SET7/9 systems. However, their study and applications in the context of nucleic acid chemistry are scarce in the literature.…”