Stepwise Sequential Redox Potential Modulation Possible on a Single Platform

Abstract

This work was supported by the Generalitat de Catalunya (2009/ SGR/00279) and the Ministerio de Ciencia e Innovación (CTQ2010-16237). A. Pepiol thanks the CSIC for a JAE grant and M. Lupu thanks the MICINN for a FPU grant. A. Pepiol and M. Lupu are enrolled in the UAB PhD program. We thank Mireia Ruis and Elena Marchante for performing the electrochemical tests. Supporting information for this article is available on the WWW under http://dx.

Towards Multifunctional Materials Incorporating Elastomers and Reversible Redox‐Active Fragments

“…In this work we describe the synthesis of a surface modifier [11] incorporating an electrochemically active metallabisdicarbollide at one end and an elastomer at the other end, and its application in the modification of a platinum electrode. Two metallacarboranes with different E 1/2 values have been prepared: one with cobalt, that is, Na [2], with E 1/2 = À2.08 V and another with iron, that is, Na[4], with E 1/2 = À0.59 V. In addition, an unexpected macrocycle with an unusual BÀC bond has been generated in total absence of a metal catalyst or an external electrophile, both with Co and Fe metallacarboranes, Na [5] and Na [6], respectively (see Scheme 1). The nature of these last two molecules is fully ascertained by X-ray structure determination, which has permitted to propose a mechanism for the formation of the macrocycle and the elastomer.…”

“…The solid was dissolved in CH 2 Cl 2 and a few droplets of acetone, acting as the soluble layer, and heptane was slowly added on the top, as the non-soluble layer. [6]: The same procedure as for Na [5] was done, but using compound 3 instead of compound 1. Weight: 18.1 mg; yield: 29 %; R f = 0.75.…”

“…Due to the paramagnetic behavior of the sample (Fe III , d 5 ), it is impossible to assign the different peaks of the NMR spectrum to each atom of the molecule. 1 H{ 11 (ÀCH 2 ÀOÀ), 60.62 (ÀCH 2 ÀOÀ), 59.60 (ÀCH 2 ÀOÀ), 26.53 ÀCH 2 À), 19.84 (ÀCH 2 À), 13.57 ppm (ÀH 2 À); IR (KBr): l = 3033.45 (w, n(C c ÀH)), 2916.80 (w, n(CÀH)), 2868.39 (w, n(CÀH)), 2529.91 (s, n(B c ÀH)), 1093.81 (s, n(CÀO)st as), 1073.12 (s, n(CÀO)st as), 969.58 cm À1 (s, n(CÀO)st sym); MALDI-TOF-MS: m/z calcd for NaC 12 [6] were obtained in the same way as described for compound Na [5].…”

“…CCDC 910883 (Na [5]) and 910884 (Na [6]) contain the supplementary crystallographic data (excluding structure factors) for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.…”

“…[5] Moreover, this sandwichlike compound has proven to be a unique framework on which the redox potential can be finely tuned in a stepwise manner. [6] Cs [COSAN] is commercially available, thermally very stable, and it is not comparatively expensive.…”