Charge-transfer hybrids containing covalently bonded polyoxometalates and ferrocenyl units

Two new charge-transfer hybrids with one or two ferrocenyl units covalently attached to a hexamolybdate cluster through an extended pi-conjugated bridge have been prepared using Pd-catalyzed coupling reactions on monoiodo- or diiodo-functionalized cluster substrates in over 60% yields. These hybrids have been characterized by (1)H NMR, FTIR, electrospray ionization mass spectrometry, and X-ray diffraction. The electronic spectra of these hybrids show a broad absorption tail extending beyond 550 nm, indicating the existence of charge-transfer transition from the ferrocenyl donor to the cluster acceptor. The observation of the clear charge-transfer transition indicates the contribution of charge-transfer resonance to the ground state in both 2a and 2b even though the donor-acceptor separation distance of 11.29 A is rather long, signaling a through-bond charge-transfer nature made possible by the organic pi-conjugated bridge. Cyclic voltammetry studies reveal a one-electron oxidation wave and a one-electron reduction wave for the hybrid with one ferrocenyl unit. For the one with two ferrocenyl units, a lower reduction potential and a two-electron oxidation wave are observed, indicating negligible electronic interactions between the two ferrocenyl units.