Step by step: The cluster [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) is an excellent platform for making a stepwise tunable redox potential system by dehydroiodination. With the addition of up to eight iodine substituents (purple; see picture), there is a fall in the E(1/2)(Co(III)/Co(II)) value from -1.80 V to -0.68 V (vs. Fc(+)/Fc; Fc = ferrocene). A practical application of this tunability has been observed in the growth of polypyrrole.
A synthetic strategy for functionalization of the three vertices of o-carborane and the attachment of the obtained triped to the solid support was developed. Further functionalization of the triped with short DNA sequences by automated DNA synthesis was achieved. The proposed methodology is a first example of boron cluster chemistry on a solid support opening new perspectives in boron cluster functionalization.
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.
The metallacarborane [3,3'-Co(1,2-closo-C2B9H11)2](-) has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3'-Co(1,2-closo-C2B9H7I4)2](-) is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.
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