A Redox‐Responsive Ferrocene‐Based Capsule Displaying Unusual Encapsulation‐Induced Charge‐Transfer Interactions

• Published in: Angewandte Chemie International Edition Vol. 62; no. 37; pp. e202308331 - n/a
• Main Authors: Toyama, Kazuki, Tanaka, Yuya, Yoshizawa, Michito
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 11.09.2023
• Edition: International ed. in English
• Subjects: Absorption spectra; Bent Amphiphile; Capsule; Charge transfer; Charge-Transfer Interaction; Chloranil; Dismantling; Encapsulation; Ferrocene; Redox; Redox; Capsule; Charge-Transfer Interaction; Bent Amphiphile; Ferrocene
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202308331

A ferrocene‐based capsule is spontaneously and quantitatively formed in water by the assembly of bent amphiphiles carrying two ferrocene units. The disassembly and assembly of the new organometallic capsule, with a well‐defined and highly condensed ferrocene core, are demonstrated by chemical redox stimuli in a fully reversible fashion under ambient conditions. In contrast to previously reported multiferrocene assemblies, only the present capsule efficiently encapsulates typical organic/inorganic dyes as well as electron‐accepting molecules in water. As a result, unusual host‐guest charge‐transfer (CT) interactions, displaying relatively wide absorption bands in the visible to near‐infrared region (λ=650–1350 nm), are observed upon the encapsulation of acceptors (i.e., chloranil and TCNQ). The resultant encapsulation‐induced CT interactions can be released by a redox stimulus through the disassembly of the capsule. Quantitative assembly of bent amphiphiles with two ferrocene units leads to a ferrocene‐based capsule in water. Besides redox‐responsive disassembly/assembly properties, the new capsule displays unusual host‐guest charge‐transfer (CT) interactions upon encapsulation of electron‐accepting molecules in the multi‐ferrocene cavity. The CT interactions are facilely dissociated by a redox‐triggered stimulus.