Thiophene‐Coated Functionalized M₁₂L₂₄ Spheres: Synthesis, Characterization, and Electrochemical Properties

Abstract

Instant balls: Well‐defined thiophene‐coated functional nanospheres were synthesized by instantaneous self‐assembly of twelve 90° PdII‐containing compounds and twenty‐four 120° organic bidentate ligands in acetone. This solvent system was efficient to prepare the self‐assembled complexes, facilitating isolation and purification. The self‐assembled functional nanospheres exhibited interesting electrochemical properties.

Metal-driven self-assembly: the case of redox-active discrete architectures

“…With a similar objective to decorate the outer surface of a metalla-structure, R. Yang et al described the M 12 L 24 sphere 34 (Scheme 5b) which integrates 24 thiophene units. 48 The investigation of the electrochemical properties of 34 in DMSO is characterized by a reduction process at E = À1.06 V vs. Ag/AgCl. No information is provided regarding the oxidation and electropolymerization ability of this thiophene-rich system.…”

Confinement of a Au–N-heterocyclic carbene in a Pd6L12 metal–organic cage

“…32,33 It is worth noting that a new irreversible cathodic potential appeared at À0.732 V, attributed to the reduction process of NO 3 À to NO 2 À within the cage, 34 perhaps owing to the change of ionic status in the cavity aer coordination. 35 The reduction current for Pd 6 L 12 were acquired at scan rates of 50-200 mV s À1 , showing that two reduction waves are located below the scan rates of 100 mV s À1 (Fig. S16 †).…”

How to Control the Rate of Heterogeneous Electron Transfer across the Rim of M6L12 and M12L24 Nanospheres

“…The few reported examples concern small supramolecular assemblies where the redox probe is readily accessible or in close proximity to the electrode surface so that direct electron transfer is possible. [27][28][29] Similarly, the reported redox-active cages are supramolecular assemblies where the outer-shell of the cage is functionalized with redox probes or the building blocks themselves are redox-active. 27,[30][31] In this contribution we explore the redox-chemistry of supramolecular M6L12 and M12L24 cages with different redox-active moieties in their interior.…”

“…[27][28][29] Similarly, the reported redox-active cages are supramolecular assemblies where the outer-shell of the cage is functionalized with redox probes or the building blocks themselves are redox-active. 27,[30][31] In this contribution we explore the redox-chemistry of supramolecular M6L12 and M12L24 cages with different redox-active moieties in their interior. Detailed electrochemical studies allows the evaluation of the thermodynamics and kinetics of electron transfer from the electrode to the electrochemical probes inside the spheres.…”