[Pt]2Pb Trinuclear Systems: Impact of the Anionic Platinum Fragment on the Lead Environment and Photoluminescence

  1. Berenguer, J.R. 1
  2. Díez, A. 1
  3. Fernández, J. 1
  4. Forniés, J. 2
  5. García, A. 1
  6. Gil, B. 1
  7. Lalinde, E. 1
  8. Moreno, M.T. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2008

Volumen: 47

Número: 17

Páginas: 7703-7716

Tipo: Artículo

DOI: 10.1021/IC8006876 SCOPUS: 2-s2.0-51849108496 WoS: WOS:000258709500035 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

Resumen

A comparison of the solid structures of three novel trinuclear sandwich R2Pb systems (NBu4)2[{Pt(C≡CTol) 4}2Pb(OH2)2] 1, [{Pt(bzq) (C≡CPh)2}2Pb] 2, and (NBu4)[{Pt(bzq) (C≡CC6H4-CF3-4)2} 2Pb(O2ClO2)] 4 (NBu4[3· (O2ClO2)]) with that of the previously reported (NBu 4)2[{Pt(C6F5)4} 2Pb] 5 showed that the local environment of PbII 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, ø = 0.43, 298 K) related to the linear (5) or bent (1 Pt-Pb-Pt 149.9°) trinuclear entities. However, in complexes 2-4, that have unprecedented PbII⋯η1(C≡CR) bonding interactions and very short Pt⋯Pb and Pt⋯Pt distances, the emissive state in solid state (77 K) is attributed to a 3MLM'CT [Pt(1)π(C≡CR)→Pt(2)/Pb(sp)π*(C≡CR)] state mixed with some ππ* 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-CF 3-4)2}2Pb(O2ClO2)] 4 modified also by PbII⋯O (O2ClO2 -) contacts. © 2008 American Chemical Society.