Behavior of Constitutional Dynamic Networks: Competition, Selection, Self‐sorting in Cryptate Systems

Abstract

Understanding dynamic systems is a crucial step toward the design of complex matter. Here, we aim to study the behavior of Constitutional Dynamic Networks (CDNs) in conditions of dynamic competition, taking cryptands and metal cations as a test bed. The CDNs of cryptates were analyzed by NMR spectroscopy. The experimental results were complemented by extensive numerical simulations, based on a large amount of thermodynamic and kinetic data available in the literature for cryptates. Although the CDN's output is a result of the interplay between the individual stability constants of the complexes in a mixture, the overall effect may be governed by only one -the most thermodynamically stable member of a network. Significantly, these findings indicate that an increase in complexity (multiplicity and connectivity) of a system may, in conditions of dynamic competition, result in "simplexity", i. e. a simplification of the output of the system.

Triple Adaptation of Constitutional Dynamic Networks of Imines in Response to Micellar Agents: Internal Uptake–Interfacial Localization–Shape Transition

“…The implementation of compounds forming different types of micelles is expected to result in different outcomes of such adaptation depending on the CDN constitution and on the micellar system used, opening the way toward the generation of different dynamic patterns and the processing of chemical information. ,− The primary aim of this work was to analyze and better understand the behavior of CDNs under changes in microenvironmental conditions using DCvLs of imines as model systems.…”

Constitutional adaptation to pKa modulation by remote ester hydrolysis

“…6A). 28,47,48 The nal composition of DCvL6 was: 52 mM A1B2, 26 mM A1, 3 mM A1 + Lys − , 77 mM + Lys − , and 28 mM B2 (Fig. S22 and S23 †).…”

“…After first devising the most reactive components towards imination, we optimized the conditions for the hydrolysis of the AAOMe ester group. Then, the time evolution of the DCvLs was investigated, observing that they resulted in states of higher “simplexity” (simplification of the output of the system) 28 through transient states of higher complexity [enzymatic selection/transient chirality/sorting] and diversity [increased number of components/constituents]. Furthermore, such constituent selection induced emerging behaviours in the final simplified states of the libraries: micelle formation and antagonistic sorting (see below).…”

“…Aer rst devising the most reactive components towards imination, we optimized the conditions for the hydrolysis of the AAOMe ester group. Then, the time evolution of the DCvLs was investigated, observing that they resulted in states of higher "simplexity" (simplication of the output of the system) 28…”

Metal and Proton Relay-Controlled Hierarchical Multistep Switching Cascade

“…This biologically relevant process and the proton relay it enables were later used by us in designing synthetic systems that exhibit intermolecular communication, catalysis-based amplification, and negative feedback loop function . These examples of intermolecular communication are some of the most complicated, molecular switch-based , synthetic reaction cascades reported, which have recently been supplemented by systems where a combination of metal redox, exchange, and relay are used to communicate between up to three species. − These latter systems, while beautiful, rely on well-established, and sometimes structurally intricate, metal coordination motifs. − Considering the importance of metal exchange and relays (including of protons) in biological systems and the limited structural space of synthetic systems that can mimic such processes, there is a critical need to explore and develop alternative systems that can accomplish similar goals. Here, we report on a hydrazone-based hierarchical multistep switching cascade that combines metal exchange and CCD-induced proton relay (Figure ).…”