Molecular Networks in Dynamic Multilevel Systems

Abstract

Dynamic multilevel systems can be assembled from molecular building blocks through two or more reversible reactions that form covalent bonds. Molecular networks of dynamic multilevel systems can exhibit different connectivities between nodes. The design and creation of molecular networks in multilevel systems require control of the crossed reactivity of the functional groups (how to connect nodes) and the conditions of the reactions (when to connect nodes). In recent years, the combination of orthogonal and communicating reactions, which can be simultaneous or individually activated, has produced a variety of systems that have given rise to macrocycles and cages, as well as molecular motors and multicomponent architectures on surfaces. A given set of reactions can lead to systems with unique responsiveness, compositions, and functions as a result of the relative reactivities. In this Concept article, different molecular networks from synthetic systems that can be produced by combinations of different reaction types are discussed. Moreover, applications of this chemistry are highlighted, and future perspectives are envisioned.

Tuning the Solubility of Self-Assembled Fluorescent Aromatic Cages Using Functionalized Amino Acid Building Blocks

“…The use of disulfide bonds, reversible through inter alia thiolate substitution, in the generation of complex supramolecular architectures has received much attention (Otto, 2012; Black et al, 2014; Sobczak et al, 2018), except those of cage topology that are still isolated cases in the literature (Sarma et al, 2007; Stefankiewicz et al, 2012; Stefankiewicz and Sanders, 2013; Naini et al, 2014). The nature of dynamic systems based on imine and disulfide bonds is thus well-known separately but multi-dynamic systems that employs them simultaneously are an enduring challenge (Sarma et al, 2007; Orrillo et al, 2019; Reuther et al, 2019).…”

Activated Self‐Resolution and Error‐Correction in Catalytic Reaction Networks**

“…[2][3][4] By studying the systems chemistry of small molecule models, important insights into emergence of life-like behavior in prebiotic settings can be achieved. [5] Significant advances in the design of synthetic systems capable of, for example, self-replication, [2,[6][7][8] selforganization, [9][10][11] self-sorting, [12][13][14] and compartmentalization, [15,16] have all been made in recent years. One area of systems chemistry that has received particular attention is emergent catalytic and autocatalytic behavior, since catalysis is perceived to be a crucial component in virtually all origin-of-life models.…”

Activated Self-Resolution and Error-Correction in Catalytic Reaction Networks

“…[2][3][4] By studying the systems chemistry of small molecule models, important insights into emergence of life-like behavior in prebiotic settings can be achieved. [5] Significant advances in the design of synthetic systems capable of, for example, selfreplication, [2,[6][7][8] self-organization, [9][10][11] self-sorting, [12][13][14] and compartmentalization, [15,16] have all been made in recent years. One area of systems chemistry that has received particular attention is emergent catalytic and autocatalytic behavior, since catalysis is perceived to be a crucial component in virtually all origin-of-life models.…”