2026-06-29T16:53:41Zhttps://docta.ucm.es/rest/oai/request

oai:docta.ucm.es:20.500.14352/1259362025-11-13T00:48:32Zcom_20.500.14352_14col_20.500.14352_15

Thermally Activated Stereoinversion in Benzotrithiophene-Based Supramolecular Polymers withWater as the Effector Naranjo Calderón, Cristina Sánchez Martín, Luis López-Gandul, Lucía Fernández Alarcón, Alberto Casellas, Nicolás M. Calbo, Joaquín Ortí, Enrique García Iglesias, Miguel 547 Química orgánica (Química) 2306 Química Orgánica We report the synthesis of the chiral benzotrithiophene (BTT) derivative 1, which self-assembles into helicalsupramolecular polymers. The C3 symmetry of BTT 1 enables a unique temperature-dependent stereomutation process inwhich water acts as a key effector. Circular dichroism measurements reveal that a higher water content induces a doublestereomutation, ultimately restoring the original helicity. In contrast, reducing the water content leads to a single, stablestereomutation, which duration depends on the amount of water in solution. To elucidate the stereomutation mechanism,we conducted a multi-level computational study, identifying two main conformations for the monomeric species that leadto diastereomeric helices with different preferred handedness, thus resulting in opposite dichroic patterns. The transitionbetween these aggregates involves rotation of the BTT cores and amide groups, a process significantly facilitated by watermolecules via triple hydrogen bonding within the helical stack. These findings exhibit the crucial role of the solvent inmodulating chiral supramolecular polymer structures and provide unprecedented insights into the influence of water onself-assembly and stereomutation processes Agencia Estatal de Investigación European Union NextGenerationEU Ministerio de Innovación, Ciencia y Universidades Generalitat Valenciana Banco Santander Depto. de Química Orgánica Fac. de Ciencias Químicas TRUE pub 2025-11-11T09:14:33Z 2025-11-11T09:14:33Z 2025-10-21 journal article VoR https://hdl.handle.net/20.500.14352/125936 XXXX-XXXX 10.1002/anie.202517603 eng info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-146971NB-I00/ES/MODULANDO EL AUTOENSAMBLAJE Y COENSAMBLAJE DE UNIDADES MONOMERICAS ELECTROACTIVAS. HACIA NUEVAS FUNCIONALIDADES EN POLIMEROS SUPRAMOLECULARES/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-128569NB-I00/ES/MODELIZACION COMPUTACIONAL DE MATERIALES MOLECULARES ELECTROACTIVOS: ESTRUCTURA ELECTRONICA, ORGANIZACION SUPRAMOLECULAR Y PROPIEDADES DE TRANSPORTE/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-125429NA-I00/ES/CONTROLANDO LA MACRO- Y NANO-ESTRUCTURACION DE MATERIALES AUTOENSAMBLADOS NO CENTROSIMETRICOS PARA AUMENTAR LA EFICIENCIA DE CELULAS FOTOVOLTAICAS ORGANICAS./ CNS2022-135129 TED2021-131255B-C44 CEX2021-001202-M CIAPOS/2023/316 Santander Talent Attraction Research L. López-Gandul, A. Fernández-Alarcón, N. M. Casellas, C. Naranjo, J. Calbo, E. Ortí, M. García-Iglesias, L. Sánchez, Angew. Chem. Int. Ed. 2025, e17603, https://doi.org/10.1002/anie.202517603 open access application/pdf Wiley