Chalcogen and Pnictogen Bonding-Modulated Multiple-Constituent Chiral Self-Assemblies

Abstract

Chalcogen and pnictogen-based σ-hole interactions have shown limited applications in controlling supramolecular chirality. In this work, we employed chalcogen and pnictogen bonding to control supramolecular chirality in a multiple-constituent system with modulate chiral optics. Phenyl phosphonium−selenium conjugates with electrophilic σ-hole regions were allowed to coassemble with the π-conjugated deprotonated amino acids. Control experimental and computational results evidenced that the chalcogen and pnictogen bonding formed with carboxylates induced morphological transformation from achiral membranes to chiral helical nanotubes with emerging supramolecular chirality. Also, the chiral helical architectures accomplished inverted handedness and chiroptical activities, including circular dichroism and circularly polarized luminescence. Finally, synergistic chalcogen and pnictogen bonding was employed to stabilize the charge-transfer complexation to afford ternary chiral co-assemblies with evolved chiral optics and luminescence. This work, showing the role of chalcogen and pnictogen bonding in manipulating supramolecular chirality and optics, will expand the toolbox in the fabrication and property-tuning of chiral materials containing elements of Group VA and VIA.

Hypervalent Iodine(III) Mediated Halogen Bonded Supramolecular Chiral System with Cholesteryl Naphthalimides

“…The amplification of the CD signal was confirmed by the g ‐factor [28–29] . It is known that the g abs ‐factor is related to the distance of the electronic dipole moment and the helix angle [29–30] . The CD signals were almost the same when PND and I(III) acted at the ratio of 1 : 1 and 1 : 2.…”

“…[28][29] It is known that the g abs -factor is related to the distance of the electronic dipole moment and the helix angle. [29][30] The CD signals were almost the same when PND and I(III) acted at the ratio of 1 : 1 and 1 : 2. After the addition of I(III), OND is consistent with the phenomenon of the PND system.…”

Pnictogen bonding in imide derivatives for chiral folding and self-assembly

“…Based on the above determining factors, HaB based on Br and I, ChB based on Se and Te, as well as PnB based on As and Sb were investigated more than other elements in the same groups. [10][11][12][13][14] Especially for PnB, P and Nbased donors are rarely reported due to their relatively strong electronegativity and low polarizability. 15 As a poor PnB donor, N could only exhibit positive holes when covalently attaching strong electron-withdrawing groups or coordinating to the metals.…”