Adaptation in Constitutional Dynamic Libraries and Networks, Switching between Orthogonal Metalloselection and Photoselection Processes

Constitutional dynamic libraries of hydrazones ^<b>a</b><b>A</b>^<b>b</b><b>B</b> and acylhydrazones ^<b>a</b><b>A</b>^<b>c</b><b>C</b> undergo reorganization and adaptation in response to a chemical effector (metal cations) or a physical stimulus (light). The set of hydrazones [^<b>1</b><b>A</b>^<b>1</b><b>B</b>, ^<b>1</b><b>A</b>^<b>2</b><b>B</b>, ^<b>2</b><b>A</b>^<b>1</b><b>B</b>, ^<b>2</b><b>A</b>^<b>2</b><b>B</b>] undergoes metalloselection on addition of zinc cations which drive the amplification of Zn­(^<b>1</b><b>A</b>^<b>2</b><b>B</b>)₂ by selection of the fittest component ^<b>1</b><b>A</b>^<b>2</b><b>B</b>. The set of acylhydrazones [<i>E</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b>, ^<b>1</b><b>A</b>^<b>2</b><b>C</b>, ^<b>2</b><b>A</b>^<b>1</b><b>C</b>, ^<b>2</b><b>A</b>^<b>2</b><b>C</b>] undergoes photoselection by irradiation of the system, which causes photoisomerization of <i>E</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b> into <i>Z</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b> with amplification of the latter. The set of acyl hydrazones [<i>E</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b>, ^<b>1</b><b>A</b>^<b>3</b><b>C</b>, ^<b>2</b><b>A</b>^<b>1</b><b>C</b>, ^<b>2</b><b>A</b>^<b>3</b><b>C</b>] undergoes a <i>dual adaptation</i> via component exchange and selection in response to two orthogonal external agents: a chemical effector, metal cations, and a physical stimulus, light irradiation. <i>Metalloselection</i> takes place on addition of zinc cations which drive the amplification of Zn­(^<b>1</b><b>A</b>^<b>3</b><b>C</b>)₂ by selection of the fittest constituent ^<b>1</b><b>A</b>^<b>3</b><b>C</b>. <i>Photoselection</i> is obtained on irradiation of the acylhydrazones that leads to photoisomerization from <i>E</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b> to <i>Z</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b> configuration with amplification of the latter. These changes may be represented by square constitutional dynamic networks that display up-regulation of the pairs of agonists (^<b>1</b><b>A</b>^<b>2</b><b>B</b>, ^<b>2</b><b>A</b>^<b>1</b><b>B</b>), (<i>Z</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b>, ^<b>2</b><b>A</b>^<b>2</b><b>C</b>), (^<b>1</b><b>A</b>^<b>3</b><b>C</b>, ^<b>2</b><b>A</b>^<b>1</b><b>C</b>), (<i>Z</i>-^<b>1</b><b>A</b>^<b>1</b><b>C</b>, ^<b>2</b><b>A</b>^<b>3</b><b>C</b>) and the simultaneous down-regulation of the pairs of antagonists (^<b>1</b><b>A</b>^<b>1</b><b>B</b>, ^<b>2</b><b>A</b>^<b>2</b><b>B</b>), (^<b>1</b><b>A</b>^<b>2</b><b>C</b>, ^<b>2</b><b>A</b>^<b>1</b><b>C</b>), (<i>E</i>-^<b>1</b><b>A</b>^<b>1</b><b>C,</b> ^<b>2</b><b>A</b>^<b>3</b><b>C</b>), (^<b>1</b><b>A</b>^<b>3</b><b>C</b>, ^<b>2</b><b>A</b>^<b>1</b><b>C</b>). The orthogonal dual adaptation undergone by the set of acylhydrazones amounts to a network switching process

Training a Constitutional Dynamic Network for Effector Recognition: Storage, Recall, and Erasing of Information

Constitutional dynamic libraries (CDLs) of hydrazones, acylhydrazones, and imines undergo reorganization and adaptation in response to chemical effectors (herein metal cations) via component exchange and selection. Such CDLs can be subjected to training by exposition to given effectors and keep memory of the information stored by interaction with a specific metal ion. The long-term storage of the acquired information into the set of constituents of the system allows for fast recognition on subsequent contacts with the same effector(s). Dynamic networks of constituents were designed to adapt orthogonally to different metal cations by up- and down-regulation of specific constituents in the final distribution. The memory may be erased by component exchange between the constituents so as to regenerate the initial (statistical) distribution. The libraries described represent constitutional dynamic systems capable of acting as information storage molecular devices, in which the presence of components linked by reversible covalent bonds in slow exchange and bearing adequate coordination sites allows for the adaptation to different metal ions by constitutional variation. The system thus performs information storage, recall, and erase processes

Consequences of Vibrational Strong Coupling on Supramolecular Polymerization of Porphyrins

Supramolecular polymers display interesting optoelectronic properties and, thus, deploy multiple applications based on their molecular arrangement. However, controlling supramolecular interactions to achieve a desirable molecular organization is not straightforward. Over the past decade, light–matter strong coupling has emerged as a new tool for modifying chemical and material properties. This novel approach has also been shown to alter the morphology of supramolecular organization by coupling the vibrational bands of solute and solvent to the optical modes of a Fabry–Perot cavity (vibrational strong coupling, VSC). Here, we study the effect of VSC on the supramolecular polymerization of chiral zinc-porphyrins (S-Zn) via a cooperative effect. Electronic circular dichroism (ECD) measurements indicate that the elongation temperature (Te) of the supramolecular polymerization is lowered by ∼10 °C under VSC. We have also generalized this effect by exploring other supramolecular systems under strong coupling conditions. The results indicate that the solute–solvent interactions are modified under VSC, which destabilizes the nuclei of the supramolecular polymer at higher temperatures. These findings demonstrate that the VSC can indeed be used as a tool to control the energy landscape of supramolecular polymerization. Furthermore, we use this unique approach to switch between the states formed under ON- and OFF-resonance conditions, achieved by simply tuning the optical cavity in and out of resonance