Synthesis and Electrochemical Anion-Sensing Properties of a Biferrocenyl-Functionalized Dendrimer

Abstract

The synthesis and electrochemical anionsensing properties of a diaminobutane poly(propyleneimine) dendrimer functionalized with biferrocenyl units 2 are presented. The redox activity of the ferrocenyl centers in 2 has been characterized by cyclic voltammetry. Cyclic and square wave voltammetric investigations demonstrate that tetraferrocenyl compound 2 and the reference compound 1 show electrochemical anion-sensing action: they display a cathodic shift of the ferrocene−ferrocenium redox couple with dihydrogenphosphate and hydrogensulfate anions in solution and immobilized onto electrode surfaces.

Construction of di- and tetra-ferrocenyl spiroborate complexes from catechol building blocks and their redox behaviors

“…31 In contrast to the variety of synthetic routes to tetraferrocenyl compounds, few have been reported for dimerizations using diferrocenyl building blocks. [13][14][15] Notably, Mueller-Westerhoff used the coordination of a diferrocenyl dithiolate to a Ni center to afford a tetraferrocenyl complex. 14a In the present study, we used the coordination of a diferrocenyl catecholate to a boron center to afford K4, whose structural feature is a tetracoordinated boron anionic bridge.…”

“…Heinze et al reported dimers of mixed-valence biferrocene amino acids linked by ureylene and amide bridges, and the effects of the bridges on the potential splitting. 15 In their pioneering work, they showed that the amide bridge affects the potential splitting of the resulting tetraferrocenyl dimer (1e − /1e − /2e − process), but the ureylene bridge has not largely effected (2e − / 2e − process). A comparison of 3 and K4 in the present study revealed that linking the diferrocenyl units (FcCFc) with the spiroborate motif increased the potential spread.…”

“…Although there have been a number of reports on mixedvalence diferrocenyl compounds, few attempts to construct dimeric assemblies using them as building blocks have been reported. [13][14][15] A key aspect of this task is the design of a diferrocenyl monomer that can be dimerized using effective linkages. In their pioneering work on developing such a strategy, Heinze et al used an elaborate combination of biferrocene amino acids and ureylene amide linkages.…”

Multi-Ferrocene-Containing Silanols as Redox-Active Anion Receptors

“…In particular, receptors containing the ferrocene moiety are especially valuable as electrochemical anion sensors, since this chemically robust metallocene undergoes fast and reversible one-electron oxidation to the positively charged ferrocenium form at accessible potentials. Surprisingly, and although a wide number of ferrocene-based redox-active receptors bearing N–H groups such as amide, urea, thiourea, triazole, amidine, guanidine, and aminosilane moieties have been reported, the use of ferrocene-containing receptors incorporating the Si–OH group as an anion recognition motif remains unexplored.…”

Synthesis, characterization and electrochemical behavior of ferrocene-containing highly branched polyurethane and its application in biosensing

“…Thus, redox-active ferrocene-containing highly branched polymers are good candidates to play a key role as multielectron transfer mediators in electrochemical response processes of biological and industrial importance [20,21]. Literature survey revealed that the redox-responsive ferrocene unit has been incorporated into amide [22], urea [23], thiourea [24], dendrimers [25] and imidazole [26] moieties to construct the anion receptors with electrochemical sensing properties.…”