T. Yamase et al., INTRAMOLECULAR ENERGY-TRANSFER AND MN4+ LUMINESCENCE IN POLYOXOMETALLOMANGANATE LATTICES, Journal of the Electrochemical Society, 143(5), 1996, pp. 1678-1680
Photoexcitation of the oxygen (O)-to-metal (RS=VV: Mo, and Nb), Ligand
-to-metal charge transfer (O-->M l.m.c.t.) bands of the polyoxometallo
manganates such as K6Na2[MnW6O24]. 12H(2)O (1), K-6[MnMo9O32]. 6H(2)O
(2), and Na-12[Mn(Nb6O19)(2)]. 50H(2)O (3) leads to an intramolecular
energy transfer from O-->M l.m.c.t. triplet states into Mn4+,followed
by the luminescence of the (2)E-->(4)A(2) transition. Quantum yield of
the Mn4+ luminescence is discussed in terms of both hydrogen bonding
at the MnO5 octahedron and the disparity of the electronic configurati
ons between the excited and ground states for the ligands of condensed
MO(6) octahedra. The thermal quenching temperatures of the Mn4+ lumin
escence for complexes 1, 2, and 3 were around 50, 350, and 200 K, resp
ectively, which are associated with the potential expansion due to the
hydrogen bonding beyond the first coordination sphere of the central
MnO6 octahedron in the anion.