A M2L2 Redox-Active Metalla-Macrocycle Based on Electron-Rich 9-(1,3-Dithiol-2-ylidene)Fluorene

Abstract

A redox-active M 2 L 2 metalla-macrocycle is depicted, of which construction has been achieved through coordination driven self-assembly from an electron-rich 9-(1,3-dithiol-2-ylidene)fluorene bis-pyridyl ligand and a cis-blocked square planar palladium complex (Pd(dppf)OTf 2 , dppf = 1,1 -Bis(diphenylphosphino)ferrocene). The resulting metalla-macrocycle has been fully characterized in solution, as well as in the solid state (X-ray crystal structure). Its electronic properties show that both constitutive ligands can be oxidized independently through a one-electron process.

Metalla‐Assembled Electron‐Rich Tweezers: Redox‐Controlled Guest Release Through Supramolecular Dimerization

“…The synthesis of tweezer OxM 4 L 2 was achieved from a stoichiometric mixture of the redox‐active ligand 4PyrDTF and acceptor OxRu in MeOH at c =10 −3 m . After precipitation with Et 2 O, the resulting solid exhibits a 1 H NMR spectrum (in MeOD) with α/β‐pyridyl and fluorenyl signals shifted upfield in comparison with the starting compount 4PyrDTF as a result of metal–ligand coordination (Figure a,b).…”

“…Thes ynthesis of tweezer OxM 4 L 2 was achieved from as toichiometric mixture of the redox-active ligand 4PyrDTF [11] and acceptor OxRu [12] in MeOH at c = 10 À3 m. After precipitation with Et 2 O, the resulting solid exhibits a 1 HNMR spectrum (in MeOD) with a/b-pyridyl and fluorenyl signals shifted upfield in comparison with the starting compount 4PyrDTF as ar esult of metal-ligand coordination (Figure 2a,b). A 1 HDOSY NMR experiment ( Figure S6, Supporting Information) revealed the presence of only one discrete species in solution with ad iffusion coefficient (D)o f3 .31·10 À10 m 2 s À1 in MeOD at c = 10 À3 m.T he corresponding calculated Stokes radius of 12 is in good agreement with the formation of the expected M 4 L 2 species.…”

Synthesis, Chiroptical, and Redox Properties of Ferrocene‐Containing Optically Active Polymers

“…Since its discovery in the 1950s, ferrocene has gathered much attention in the fields of polymer chemistry, supramolecular chemistry, and organometallic chemistry due to its reactivity and redox properties . Ferrocene derivatives containing various substituents including alkyl, vinyl, amino, and carboxy groups are utilized as key components of metal‐containing molecules and building blocks of macrocycles, metallacycles, and polymers . Ferrocene‐containing polymers are promising as functional materials applicable to memory devices, rechargeable lithium batteries, catalysts, and liquid crystalline materials .…”

Metalla‐Assembled Electron‐Rich Tweezers: Redox‐Controlled Guest Release Through Supramolecular Dimerization

“…[18] This value is in good accordance with the one reported for the analogous SHexyl functionalized ligand. [11] Interestingly, both self-assembled structures OxM4L2 and (NaphM4L2)2 show a significant splitting of the oxidation wave, providing evidence of electronic interactions between DTF units. A similar splitting was already reported in the case of TTF-based molecular tweezers and was ascribed to the formation of mixed valence and -dimer species.…”

“…Remarkably, the latter can be reversibly shifted to a tweezer dimer upon oxidation, with concomitant guest release ( Figure 1). The synthesis of tweezer OxM4L2 was achieved in one-step from a stoichiometric mixture of redox active ligand 4PyrDTF [11] and arene ruthenium acceptor OxRu [12] in MeOH at C = 10 -3 M (15 h, 50°C). After precipitation with Et2O, the resulting solid exhibits a 1 H NMR spectrum (MeOD) with / pyridyl and fluorenyl signals upfield shifted in comparison with starting 4PyrDTF, as a result of the metal-ligand coordination (Figure 2a-b).…”