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Electrochemical anion sensing using electrodes chemically modified with Au(I)-Cu(I) heterotrimetallic alkynyl cluster
Antonio Doménech1, Igor O Koshevoy, Noemí Montoya
1Departament de Química Analítica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain. antonio.domenech@uv.es
Abstract:
A novel family of electrochemical anion sensors operating in aqueous media, based on the heterometallic Au(I)-Cu(I) [{Au(3)Cu(2)(C(2)R)(6)}Au(3)(PPh(2)C(6)H(4)PPh(2))(3)](PF(6))(2) (L1, R = Fc; L2, R = C(6)H(4)Fc) alkynyl cluster complexes, is presented. Upon attachment to graphite and gold electrodes, these compounds exhibit a well-defined, essentially reversible, solid-state electrochemistry in contact with aqueous media, based on ferrocenyl-centered oxidation processes involving anion insertion, leading to distinctive pH-independent electrochemical responses for fluoride, chloride, bromide, perchlorate, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, and nitrate anions. Cluster-modified electrodes can be used as potentiometric sensors as a result of the reversible, diffusion-controlled electrochemistry obtained for the anion-assisted electrochemical oxidation of L1 and L2.
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