1,5,9,13-Tetraselena[13]ferrocenophane: synthesis, complexation, crystallographic and electrochemical study

Abstract

A novel macrocyclic ferrocenophane, 1,5,9,13-tetraselena[13]ferrocenophane (L), was synthesized. Reaction of L with [M(NCMe)(4)](PF(6))(2) (M = Pd and Pt) or [Cu(NCMe)(4)](PF(6)) led to complexes [ML](PF(6))(2) (M = Pd and Pt) or [CuL](PF(6)). The Ag(i) cation induced the formation of a one-dimensional polymer {[AgL](PF(6))}(n) due to its large ionic radius. The structures of L and its four complexes have been determined by X-ray crystallography. Electrochemical studies showed that, in [ML](PF(6))(2) (M = Pd and Pt), the half-wave potential of the 1,1'-ferrocenediyl group shifts to much more positive potentials due to the strong through-space interaction between the two metals (M...Fe).

Macrocyclic Se4N2[7,7]ferrocenophane and Se2N[10]ferrocenophane containing benzyl unit: synthesis, complexation, crystal structures, electrochemical and optical properties

“…The ferrocene unit adopts a synclinal conformation with a torsion angle C1–Cg1–Cg2–C6 (Cg is the centroid of the Cp ring) of 27.67°, much smaller than that in 1,5,9,25,29-hexaselena[9,9]ferrocenophane (163.67°) 57 or in L2 (70.29°). The dihedral angle of two Cp rings (3.35°) is also smaller than that of 1,5-diselena[5]ferrocenophanes (8.52°) 23 or L2 (5.83°), which may be the result of flexibility of the large ring.…”

“…Cu + prefers a tetrahedral geometry whereas Cu 2+ does typically a square pyramid or a trigonal bipyramid in some biosystems. 23,61–63 Therefore, during the formation of 4 , Cu 2+ induces the oxidation of ferrocene units in L1 and forms a stable Cu + complex, more information can be obtained from UV-vis spectrometric and electrochemical studies. However, no significant change in structural parameters was observed between the ferrocene unit in 3 and the ferrocenium unit in 4 .…”

“…Cu + prefers a tetrahedral geometry whereas Cu 2+ does typically a square pyramid or a trigonal bipyramid in some biosystems. 23,[61][62][63] Therefore, during the formation of 4, Cu 2+ induces the oxidation of ferrocene units in L1 and forms a stable Cu +…”

Oxygen, sulfur, selenium, tellurium and polonium

“…56 The macrocyclic ferrocenophane derivative of 16-crown-4 featuring selenoether donor groups (71) was prepared and the corresponding Pd, Pt, Cu and Ag complexes synthesised. 57 The Pd, Pt and Cu complexes were monomeric, while the Ag species was polymeric. The 26,28-ditellurasapphyrin (72) and 30,33-ditelluraubyrin (73) and 21,23ditelluraporphyrins ( 74) have been synthesised.…”

A novel macrocyclic diselenoether containing naphathalene ring and its Mo(0) tetracarbonyl complex: Synthesis, crystal structures and fluorescence study

“…There is no stable complex isolated that has this kind of selena-macrocycles as a ligand. In our group, a series of macrocyclic polyselena[n]ferrocenophanes have been synthesized and studied, which display strong affinities with soft Lewis metals [8][9][10][11]. In light of this, we now initiate the systematic study of selenamacrocycles incorporating fluorophore.…”