Patterned functionalization of gold and single crystal silicon via photochemical reaction of surface-confined derivatives of (eta5-C5H5)Mn(CO)3

Treatment of a single crystal Si wafer (n- or p-type, 100 face) having a thin surface SiO(x) layer with Cl3Si-(eta(sup 5)- C5H4)Mn(CO)3, I, yields the Si-confined complex (Si)-O-Si- (eta(sup 5)- C5H4)Mn(CO)3. Coverage of about a monolayer is typically achieved. Near-UV irradiation of the Si-confined tricarbonyl in L = PPh2(n-octyl) gives the surface-confined substitution product (Si)-O-Si- (eta(sup 5)- C5H4)Mn(CO)2L. The identities of the Si-confined complexes were determined by comparison of their IR CO stretching frequencies with those of (CH3)3Si- (eta(sup 5)- C5H4)Mn(CO)2L, and of the corresponding high surface area SiO2-confined species, (SiO2)-O-Si (CH3)2-(eta(sup 5)- C5H4)Mn(CO)2L (L = CO, PPh(n-octyl)). Treatment of a Au-coated Si wafer with HS(CH2)11- (eta(sup 5)- C5H4)Mn(CO)3, II, yields about a monolayer of the Au-confined complex (Au)-S(CH2)11- (eta(sup 5)- C5H4)Mn(CO)3. Near-UV irradiation of the Au-confined tricarbonyl in the presence of L = PPh2(n-octyl) yields the surface-confined substitution product (Au)-S(CH2)11- (eta(sup 5)- C5H4)MN(CO)2L. The photochemistries of surface-confined I and II differ from the photochemistries of the corresponding solution species. Patterning of the surface of a Si wafer modified with I or of Au modified with II is readily accomplished, since photosubstitution occurs only on irradiated portions of the surface.