Oxidation triggers guest dissociation during reorganization of an FeII4L₆twisted parallelogram

Abstract

A three-dimensional FeII4L6 parallelogram was prepared from ferrocene-containing ditopic ligands. The steric preference of the bulky ferrocene cores towards meridional vertex coordination brought about this new structure type, in which...

Self‐Assembly of a Redox Active, Metallosupramolecular [Pd3L6]6+ Complex Using a Rotationally Flexible Ferrocene Ligand

“…While the cage was redox active, addition of the guest had no effect on the redox potential. The current work, coupled with other recent studies, [15,24] strengthens the postulate that rotational flexible 1,1′‐disubstituted ferrocene ligands can be reliably used to assemble discrete, cavity containing, metallosupramolecular architectures. Due the rotational flexibility of L 4EFc a wide range of [Pd n ( L 4EFc ) 2n ] 2n+ assemblies were theoretically possible but only [Pd 3 ( L 4EFc ) 6 ] 6+ is formed quantitively.…”

“…More recently, Nitschke and co‐workers detailed the formation of an [Fe 4 (L) 6 ] 8+ twisted parallelogram from 1,1′‐bis(4‐aminophenyl)ferrocene, 2‐formylpyridine and Fe(II) ions [16] . A similar outcome was achieved using a related ferrocene ligand where a diazo unit replace the imine linker.…”

Emerging Spacers‐Based Ligands for Supramolecular Coordination Complexes

“…Nitschke and co‐workers reported ionic, Fe(II)‐based cages containing four ferrocene spacer motifs [44] . The cage [ 15 ] 8+ was obtained from a neutral ditopic ferrocene spacer based ligand (L 15 ) and Fe(II) ion.…”

Electrochemical Recognition of Aromatic Species with Ferrocenylated 1,3,5‐Triazine‐ or 1,3,5‐Triphenylbenzene‐Containing Highly Organized Molecules

“…[20][21][22][23] In the last several years, interesting works dealing with the preparation of Fc containing molecular cages were published. [24][25][26][27][28][29][30][31][32][33][34] From the viewpoint of the construction of these highly organized molecules, Fc offers interesting perspectives related to a dynamic flexibility of the cyclopentadienyl rings (anti or syn rotation phenomenon). Most commonly, organized molecules composed of 1,1'-disubstituted ferrocenes adopting the syn conformation were reported.…”

“…[28][29][30][31][32][33][34] However, some specific Fc based ligands, such as rotationally flexible ones, [24,25,33,34] offered the possibility to construct either cage structures in which 1,1'disubstituted ferrocenes adopted the anti conformation [24,25] or intriguing low-symmetry architectures in which 1,1'-disubstituted Fc's cyclopentadienyl rings were twisted. [26] Additionally, cage products that feature a confined cavity motif were shown to incorporate some specific guest molecules, such as ptoluenesulfonate anion. [24,32] Importantly, chemical oxidation assays [26] (formation of Fc + ) revealed that redox activity is assured in such specific cage products; However, preliminary electrochemical trials suggested that host-guest inclusion process might not cause the drastic changes in redox potentials of the cage.…”