FORMATION OF METAL-CLUSTERS ON THE SURFACES OF COVALENTLY BOUND SELF-ASSEMBLED LIGAND MONOLAYERS

This paper describes interactions between metal complexes and self-ass emblies of covalently bound ligand monolayers on surfaces. Covalently bound molecular self-assemblies of (3-cyanopropyl) trichlorosilane (CP TS) were anchored on the surfaces of fused quartz and the native oxide of the [100] crystallographic orientation of p-doped Si wafers. The f ormations of a number of ruthenium and osmium metal carbonyl complexes on both the substrates and substrates coated with ligand monolayers h ave been examined with polarized variable-angle internal attenuated to tal reflection infrared spectroscopy (PVAI-ATR-IR). Both mononuclear s pecies M(CO)(n)L (n = 2,3), where L = -(CH2)3CN, ana multinuclear spec ies M3(CO)10(mu-CO)L were observed on the surface of the covalently bo und, self-assembled ligand monolayers when the coated substrates were treated with M3(CO)12, where M = Ru and Os. Ruthenium porphyrin macroc ycle RuTPP(CO).THF which has a ''disklike'' structure was bound to a C PTS axial ligand and then formed a covalently bound, self-assembled mo nolayer of ''porphyrin-disk'' stacking on the quartz surface. This mon olayer was analyzed by UV-vis spectroscopy and secondary ion mass spec trometry (SIMS).