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Carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) (CBF) is a widely used insecticide. Traditional methods like hydrolysis and direct photolysis cannot remove CBF effectively. In this study, the photodecay of 0.1 mM CBF in UV/H2O2, UV/S2O8(2-), and UV/H2O2/S2O8(2-) and sequential addition of a second oxidant were studied under UV light at 254 nm. The degradations of CBF follow pseudo-first-order decay kinetics. Direct photolysis was slow, but the corresponding degradation rate was increased with the addition of hydrogen peroxide (H2O2) or potassium peroxydisulfate (K2S2O8). In the UV/H2O2 reaction, the optimum reaction rate was 0.9841 min-1 at 10 mM H2O2 (pH 7); however, retardation is observed if H2O2 is overdosed. Such retardation is not observed in the UV/S2O8(2-) system, but a nonlinear increment of removal efficiency is identified. The UV/H2O2/S2O8(2-) process on the other hand shows the best performance in CBF degradation, but it has a less effective mineralization than that of the sole UV/S2O8(2-) reaction.

A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C)Fe(C(5)Me(5))(dppe)], 1, and its oxidized species, [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C)Fe(C(5)Me(5))(dppe)][PF(6)], 2, have been synthesized and their X-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond](H)C[double bond]C)Fe(C(5)Me(5))(dppe)][PF(6)], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at -1.49 V (vs SCE), a fully reversible oxidation at -0.19 V, and a quasireversible oxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C)Fe(C(5)H(5))(dHpe) (Cp = C(5)H(5), dHpe = H(2)P[bond](CH(2))(2)[bond]PH(2)) (1-H) show that the LUMO is mainly bipyridine ligand pi* in character while the HOMO is largely iron(II) d orbital in character. The electronic absorption spectrum of 1 shows low-energy absorption at 390 nm with a 420 nm shoulder in CH(2)Cl(2), while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additional low-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(I)-alkynyl complex [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C[bond]H)], 4, complex 1 is found to be nonemissive, and such a phenomenon is attributed to an intramolecular quenching of the emissive d pi(Re) --> pi*(bpy) (3)MLCT state by the low-lying MLCT and LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from the d pi(Re) --> pi*(bpy) (3)MLCT state can be demonstrated in the oxidized species 2 and the related vinylidene analogue 3 due to the absence of the quenching pathway.