A comparison of the solid structures of three novel trinuclear sandwich Pt2Pb systems (NBu4)(2)[(Pt(C=CTol)(4)}(2)Pb(OH2)(2)] 1, [(Pt(bzq)(C CPh)(2))(2)Pb] 2, and (NBu4)[{Pt(bzq)(C CC6H4-CF3-4)(2)}(2)Pb(O2ClO2)] 4 (NBu4[3 center dot(O2ClO2)]) with that of the previously reported (NBu4)(2)[Pt(C6F5)(4))(2)Pb] 5 showed that the local environment of Pb-II is highly sensitive to the nature of the anionic platinate(II) precursors. The photoluminescence (PL) studies of all 1-5 complexes revealed a dependence of PL on the structure type. Thus, complexes 1 and 5 exhibit metal centered emissions (1, 497 nm, 77 K; 5, 539 nm, phi = 0.43, 298 K) related to the linear (5) or bent (1 Pt-Pb-Pt 149.9 degrees) trinuclear entities. However, in complexes 2-4, that have unprecedented Pb-II... eta(1)(C CR) bonding interactions and very short Pt center dot center dot center dot Pb and Pt center dot center dot center dot Pt distances, the emissive state in solid state (77 K) is attributed to a (MLM)-M-3'CT [Pt(1)pi(C CR)-> Pt(2)/Pb(sp)pi*(C CR)] state mixed with some pi pi* excimeric character in neutral complexes 2 (R = Ph) and 3 (R = C6H4-CF3-4), and in the case of the adduct (NBu4)[{Pt(bzq)(C CC6H4-CF3-4)(2)}(2)Pb(O2ClO2)] 4 modified also by Pb-II center dot center dot center dot O (O2ClO2-) contacts.