Tuning Supramolecular Polymer Assembly through Stereoelectronic Interactions.
J Am Chem Soc
; 143(32): 12688-12698, 2021 08 18.
Article
en En
| MEDLINE
| ID: mdl-34346675
ABSTRACT
The supramolecular polymerization of 2,11-dithia[3.3]paracyclophanes through self-complementary intermolecular and transannular amide hydrogen bonding is presented. An n â π* interaction between the amide hydrogen bonding units and the central bridging atom results from the single-point exchange of a carbon atom for a sulfur atom. This orbital donor-acceptor interaction can be strengthened by oxidizing the sulfide to a sulfone which acts to shorten the donor···acceptor distance and increase orbital overlap. Experimental signatures of the increased n â π* interaction include larger isodesmic polymerization elongation constants in solution, changes in characteristic bond stretching frequencies, and geometric/structural changes evaluated by X-ray crystallography. The experimental data are supported by extensive computational investigations of both assembling and nonassembling 2,11-dithia[3.3]paracyclophanes as well as a rationally designed model system to confirm the role of stereoelectronic effects on supramolecular polymer assembly.
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1
Banco de datos:
MEDLINE
Asunto principal:
Polímeros
Tipo de estudio:
Prognostic_studies
Idioma:
En
Año:
2021
Tipo del documento:
Article