[Abstract] We present herein the synthesis of a new polycationic pseudo[1]rotaxane, self-assembled in excellent yield through hydrazone bonds in aqueous media of three different aldehyde and hydrazine building blocks. A thermodynamically controlled process has been studied sequentially by analyzing the [1 + 1] reaction of a bisaldehyde and a trishydrazine leading to the macrocyclic part of the system, the ability of this species to act as a molecular receptor, the conversion of a hydrazine-pending cyclophane into the pseudo[1]rotaxane and, lastly, the one-pot [1 + 1 + 1] condensation process. The latter was found to smoothly produce the target molecule through an integrative social self-sorting process, a species that was found to behave in water as a discrete self-inclusion complex below 2.5 mM concentration and to form supramolecular aggregates in the 2.5–70 mM range. Furthermore, we demonstrate how the abnormal kinetic stability of the hydrazone bonds on the macrocycle annulus can be advantageously used for the conversion of the obtained pseudo[1]rotaxane into other exo-functionalized macrocyclic species.The authors are thankful for the funding received from the MCIN/AEI/10.13039/501100011033 and ERDF “A way of making Europe” (CTQ2016-75629-P, CTQ2017-89166-R and PID2019-105272GB-I00), the Consellería de Cultura, Educación e Universidade, Xunta de Galicia (ED431C 2018/39, ED431C 2022/39 and 508/2020), and the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Programme (Grant Agreement No. 851179). P.C. and A.B.-G. thank the Consellería de Cultura, Educación e Universidade, Xunta de Galicia for their PhD and postdoctoral fellowships (ED481A-2020/019 and ED481B-2021-099, respectively). M.D.-A. thanks the Fundación Gil Dávila and the Ministerio de Universidades (FPU21/06302) for his PhD fellowships. E.P. thanks the MCIN/AEI/10.13039/501100011033 and ESF “Investing in your future” for her Ramón y Cajal contract (RYC2019-027199-I)Xunta de Galicia; ED431C 2018/39Xunta de Galicia; ED431C 2022/39Xunta de Galicia; 508/2020Xunta de Galicia; ED481A-2020/019Xunta de Galicia; ED481B-2021-09
