Abstract
16 We previously reported novel fluorescent aromatic cages that are self-produced using a set of 17 orthogonal dynamic covalent reactions, operating simultaneously in one-pot, to assemble up to 10 18 components through 12 reactions into a single cage-type structure. We now introduce N-functionalized 19 amino acids as new building blocks that enable tuning the solubility and analysis of the resulting cages. 20 A convenient divergent synthetic approach was developed to tether different side chains on the N-21 terminal of a cysteine-derived building block. Our studies show that this chemical functionalization 22 does not prevent the subsequent self-assembly and effective formation of desired cages. While the 23 originally described cages required 94% DMSO, the new ones bearing hydrophobic side chains were 24 found soluble in organic solvents (up to 75% CHCl3), and those grafted with hydrophilic side chains 25 were soluble in water (up to 75% H2O). Fluorescence studies confirmed that despite cage 26 functionalisation the aggregation-induced emission properties of those architectures are retained. Thus, 27 this work significantly expands the range of solvents in which these self-assembled cage compounds 28 can be generated, which in turn should enable new applications, possibly as fluorescent sensors. 29 1 Introduction 30 Due to the unique physicochemical properties and a wide range of applications, cage-type architectures 31 enjoy unflagging interest.(Hasell and Cooper, 2016;Markiewicz et al., 2017;Beuerle and Gole, 32 2018;Mastalerz, 2018) Of the many types of cage systems, those based on reversible covalent bonds 33