Redox-switchable host–guest complexes of metallocenes and [8]cycloparaphenylene

Abstract

The cycloparaphenylene (CPP) nanocarbons are an appealing family of macrocyclic organic semiconductors with size-tunable structures and unique optoelectronic properties, which can be further modulated by complexation with guest molecules. While...

Side-Chain Type Ferrocene Macrocycles

“…In the case of A 2 B ( A 3 see Figure S12), the distance between hydrogen atoms and aromatic planes ( d PLN ), the distance between the carbon atoms and the center of the aromatic planes ( d C–X ), and the angle at the hydrogen (∠C–H–X) (X represents the centroid of the phenyl) are measured to be 3.1 4.0, and 147.2°, respectively. These values align perfectly with the established C–H−π criteria, demonstrating the presence of these interactions. , Notably, this observation is consistent with the host–guest complexes of Fc⊂[8]­cycloparaphenylenes (CPP) that have been recently reported …”

“…59,60 Notably, this observation is consistent with the host−guest complexes of Fc⊂ [8]cycloparaphenylenes (CPP) that have been recently reported. 61 ■ REDOX AND PHOTOPHYSICAL PROPERTIES For multiferrocenyl cyclic systems, electrochemistry serves as a conventional tool for assessing the electronic communication between redox sites. 62,63 In this regard, the redox properties of A 2 B and A 3 were investigated by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV).…”

Ferrocene: an exotic building block for supramolecular assemblies

“…47 In an aqueous medium, C6A binds to both Fc and Fc + , with Fc + showing a stronger binding affinity compared to Fc. 6 Furthermore, several other hosts, such as cyclo[6]aramide, 48 [8]cycloparaphenylene (CCP) 49 and cyclobis(paraquat- p -phenylene) (CBPQT 4+ ), 50 have been very recently identified for Fc. Among all the macrocyclic hosts, CB7 exhibits the highest binding affinity for Fc.…”

“…(iv) Fc in out-of-equilibrium gels Fc has also been utilized in developing far-from-equilibrium assemblies due to its facile redox-reversibility and host-guest complexation ability. A far-from-equilibrium self-assembly has been created using stearic acid (48) and a redox sensitive base, Fc-NMe 2 (49), that acts as a building block and a fuel (Fig. 9a).…”

“…9a). However, this sol returns to the gel state by adding more fuel (49), leading to the temporal self-assembled gel state. The activation (i.e., acidbase neutralization, followed by gelation) and deactivation (oxidation of Fc) steps worked in an orthogonal fashion where the first step is faster than the latter one, resulting in development of transient assemblies under dissipative conditions.…”