RT Journal Article
T1 Intramolecular transamidation enables one-pot synthesis of three chiral, Z-shaped perilenediimides for null-type supramolecular polymer formation
A1 Sánchez Martín, Luis
A1 Carreño Hernández, Adrián
A1 Schwalb Freire, Alfonso José
A1 García Melo, Fátima
AB Building on the concept of null-type supramolecular polymers, we present herein the synthesis of three isomeric Z-shaped perylenediimides (Z-PDIs 1–3), in which a central PDI core is linked to peripheral trisdodecyloxybenzamide groups by an alanine-derived linker. Interestingly, we discovered that both the starting amines used in the synthesis of symmetric Z-PDIs 1 and 3 can undergo intramolecular transamidation, allowing the one-pot generation of all three isomers 1–3. The self-assembly behavior of these compounds was systematically explored using various spectroscopic methods. In line with our previous observations, the UV-Vis spectra of the aggregates closely resemble those of their monomeric forms, confirming the formation of null-type supramolecular polymers. Moreover, we found that the position of the stereogenic center strongly affects the aggregate stability: the assemblies become more stable when the stereocenter is positioned farther to the PDI core. The lateral benzamide groups facilitate kinetically controlled polymerization through the formation of intramolecular hydrogen-bonded pseudocycles, with the stereocenter's location again playing a key role in modulating the assembly kinetics. Finally, we demonstrate an efficient transfer of point chirality from the alanine-derived linker to the supramolecular structure, resulting in the formation of chiral null-type supramolecular polymers.
PB Royal Society of Chemistry
YR 2025
FD 2025-11-26
LK https://hdl.handle.net/20.500.14352/132594
UL https://hdl.handle.net/20.500.14352/132594
LA eng
NO J. Schwalb, A. Carreño, F. García, L. Sánchez. Intramolecular transamidation enables one-pot synthesis of three chiral, Z-shaped perilenediimides for null-type supramolecular polymer formation. Chem. Sci., 2026, 17, 2627–2636.
NO Ministerio de Ciencia e Inovación (España)
NO Agencia Estatal de Investigación (España)
DS Docta Complutense
RD 26 feb 2026