title: [Pt]2Pb trinuclear systems: impact of the anionic platinum fragment on the lead environment and photoluminescence.
abstract: A comparison of the solid structures of three novel trinuclear sandwich Pt 2Pb systems (NBu 4) 2[{Pt(C identical withCTol) 4} 2Pb(OH 2) 2] 1, [{Pt(bzq)(C identical withCPh) 2} 2Pb] 2, and (NBu 4)[{Pt(bzq)(C identical withCC 6H 4-CF 3-4) 2} 2Pb(O 2ClO 2)] 4 (NBu 4[ 3.(O 2ClO 2)]) with that of the previously reported (NBu 4) 2[{Pt(C 6F 5) 4} 2Pb] 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, varphi = 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 identical withCR) bonding interactions and very short Pt...Pb and Pt...Pt distances, the emissive state in solid state (77 K) is attributed to a (3)MLM'CT [Pt(1)pi(C identical withCR)-->Pt(2)/Pb(sp)pi*(C identical withCR)] state mixed with some pipi* excimeric character in neutral complexes 2 (R = Ph) and 3 (R = C 6H 4-CF 3-4), and in the case of the adduct (NBu 4)[{Pt(bzq)(C identical withCC 6H 4-CF 3-4) 2} 2Pb(O 2ClO 2)] 4 modified also by Pb (II)...O (O 2ClO 2 (-)) contacts.
authors.affiliation: Departamento de Química-Grupo de Síntesis Química de La Rioja, UA-CSIC, Universidad de La Rioja, 26006, Logroño, Spain. elena.lalinde@unirioja.es
authors.forename: Jesús Rubén
authors.initials: JR
authors.lastname: Berenguer
authors.forename: Alvaro
authors.initials: A
authors.lastname: Díez
authors.forename: Julio
authors.initials: J
authors.lastname: Fernández
authors.forename: Juan
authors.initials: J
authors.lastname: Forniés
authors.forename: Ana
authors.initials: A
authors.lastname: García
authors.forename: Belén
authors.initials: B
authors.lastname: Gil
authors.forename: Elena
authors.initials: E
authors.lastname: Lalinde
authors.forename: M Teresa
authors.initials: MT
authors.lastname: Moreno