Consecutive complex aggregation pathway in covalent helical polymer-metal complexes: nanospheres with controlled P/M macroscopic chirality

Tarrío, Juan JoséHermida, BorjaRodríguez Riego, RafaelCrassous, JeanneQuiñoá Cabana, EmilioFreire Iribarne, Félix Manuel2025-05-022025-05-022024-12Tarrío, J. J., Hermida, B., Rodríguez, R., Crassous, J., Quiñoá, E., Freire, F. (2024). Consecutive Complex Aggregation Pathway in Covalent Helical Polymer‐Metal Complexes: Nanospheres with Controlled P/M Macroscopic Chirality. "Small", vol. 21. nº 71613-6810https://hdl.handle.net/10347/41164Kinetically trapped and thermodynamic nanospheres with opposite macroscopic P/M chirality and opposite circularly polarized luminescence (CPL) can be obtained from a single helical polymer-metal complex under the same environmental conditions. To prepare these nanospheres, a chiral poly(diphenylacetylene) (PDPA) [poly-(L)-1] with a large energy barrier between the P and M helical senses is chosen as source of chirality, while Ba2+ metal ions are selected as crosslinking agents. As a result, the poly-(L)-1/Ba2+ complex can generate both kinetically trapped (Agg1, M nanospheres) and thermodynamic (Agg2, P nanospheres) aggregates, which can be dispersed in the same solvent. Due to the high energy barrier of the helix inversion process for poly-(L)-1, the complete evolution from the kinetically trapped aggregate (Agg1, M nanospheres) to the thermodynamic one (Agg2, P nanospheres) takes more than 75 days at room temperature, which can be accelerated at higher temperatures. These nanospheres are stable and remain dispersed in solution for up to 8 months without further aggregation.eng© 2024The Author(s). Small published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. Attribution-NonCommercial 4.0 Internationalhttp://creativecommons.org/licenses/by-nc/4.0/ChiralityCPLDynamic MacroscopicHelical Polymer-metal ComplexesNanospheres Consecutive Mechanism2306 Química orgánicaConsecutive complex aggregation pathway in covalent helical polymer-metal complexes: nanospheres with controlled P/M macroscopic chiralityjournal article10.1002/smll.2024093791613-6829open access