An original electrochemical synthesis of {[Rh4(mu-OOCCH3)4(phen)4]2+}n (1) molecular wire films from a solution of binuclear bridged Rh complexes [Rh2(mu-OOCCH3)2(phen)2(X)2](Y)2 (X = H2O, Y = BF4(-) (2a) and X = CH3CN, Y = BF4(-) (2b)) in MeCN electrolyte is reported. UV-vis spectroscopy and quartz crystal microbalance electrochemical coupled techniques have been used to demonstrate the electrosynthesis process. The resulting polymetallic compound has been characterized on the basis of its physicochemical properties, which have been compared with those of a chemically synthesized sample. Furthermore, according to EPR, 1H NMR and electrochemical behaviour, the mechanism of the oxidation of this polymetallic wire, containing mixed valent rhodium centers and alternatively acetate bridged Rh-Rh bonds, has been investigated in detail.

= 4,4Ј-dimethyl-2,2Ј-bipyridine) were synthesized and characterized with spectroscopic methods. The structure of complex 2 was determined by using X-ray crystallography. The rhodium atoms in compound 2 have distorted octahedral coordination with O and N atoms in equatorial positions and a Rh atom and a H 2 O molecule in axial coordination sites. Reduction of compound 2 with aqueous alcohols leads to the formation of the molecular wire {[Rh 2 (µ-OOCCH 3 ) 2 (dmbpy) 2 ][BF 4 ]} n ·2nH 2 O (3) con-

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