2026-04-17T06:39:59Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/86102024-02-08T01:05:27Zcom_10259_3592com_10259_3591com_10259.4_106com_10259_2604com_10259_3924com_10259_5086col_10259_3930col_10259_3925

Matarranz, Beatriz Díaz Cabrera, Sandra Ghosh, Goutam Carreira Barral, Israel Soberats, Bartolomé García Valverde, María Quesada Pato, Roberto Fernández, Gustavo 2024-02-07T08:20:25Z 2024-02-07T08:20:25Z 2023-02 1433-7851 http://hdl.handle.net/10259/8610 10.1002/anie.202218555 1521-3773 After more than three decades of extensive investigations on supramolecular polymers, strategies for self-limiting growth still remain challenging. Herein, we exploit a new V-shaped monomer design to achieve anticooperatively formed oligomers with superior robustness and high luminescence. In toluene, the monomer-oligomer equilibrium is shifted to the monomer side, enabling the elucidation of the molecular packing modes and the resulting (weak) anticooperativity. Steric effects associated with an antiparallel staircase organization of the dyes are proposed to outcompete aromatic and unconventional B−F⋅⋅⋅H−N/C interactions, restricting the growth at the stage of oligomers. In methylcyclohexane (MCH), the packing modes and the anticooperativity are preserved; however, pronounced solvophobic and chain-enwrapping effects lead to thermally ultrastable oligomers. Our results shed light on understanding anticooperative effects and restricted growth in self-assembly. We thank the Deutsche Forschungsgemeinschaft (SFB858) for funding (B.M. and G.F.). B.S. thanks the MICINN/AEI of Spain for the projects EQC2018-004206-P, RED2018-102331-T, PID2019-107779GA-I00/AEI/10.13039/501100011033 and RYC-2017-21789. M. G.-V. and R.Q. thank funding from Consejería de Educación de la Junta de Castilla y León and ERDF (project BU067P20) and MICN/AEI/10.13039/501100011033 (grant PID2020-117610RB-100). S.D.-C. and I.C.-B. thank Consejería de Educación de la Junta de Castilla y León, ERDF (European Regional Development Fund) and European Social Fund for their pre- and post-doctoral contracts, respectively.Conflict of Interest Open Access funding enabled and organized by Projekt DEAL. application/pdf eng Wiley Angewandte Chemie International Edition. 2023, V. 62, n. 17 https://doi.org/10.1002/anie.202218555 Atribución-NoComercial 4.0 Internacional http://creativecommons.org/licenses/by-nc/4.0/ info:eu-repo/semantics/openAccess Química orgánica Bioquímica Biología molecular Chemistry, Organic Biochemistry Molecular biology Anticooperative Supramolecular Oligomerization Mediated by V‐Shaped Monomer Design and Unconventional Hydrogen Bonds info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Angewandte Chemie International Edition 62 17