Coordinated halide and pseudo halide‐dependent structures and photoluminescence of defective double cubane Zn(II) clusters

Toshiaki Kuramitsu (1) , Sotaro Kusumoto (1) , Hitomi Ohmagari (2) , Miki Hasegawa (2) , Pierre Thuéry (3) , Yang Kim (1) , Shinya Hayami (1) , Masaaki Nakamura (1)

1 Department of Chemistry [Kumamoto]
2 AGU - Aoyama Gakuin University
3 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)

Tetranuclear Zn(II) complexes, [Zn4(L)4(µ3-OCH3)2(X)2] (L = 2-((benzyloxy)carbonyl)-6-methoxyphenolate; X = Cl ⎻ (1), Br ⎻ (2), I ⎻ (3), N3 ⎻ (4), or NCS ⎻ (5)), have provided "defective" double-cubane core [Zn4O6], which were bridged by two µ3-methoxo and four µ2-phenolato oxygens in each discrete complex. In halide complexes 1, 2 and 3, two Zn(II) ions are in slightly distorted octahedral coordinations and the other two in geometries close to the severely distorted trigonal bipyramid, respectively, while all four Zn(II) in pseudo halide complexes 4 and 5 show slightly distorted octahedral geometries. Each complex exhibited blue fluorescence (λmax = 415-428 nm) with high photoluminescence quantum yields (PLQYS, Φem) in the range of 0.22-0.53 at room temperature in the solid state, of which 5 showed the highest Φem among the alkoxo-bridged multinuclear Zn(II) clusters ever reported.

Domains: Coordination chemistry; Cristallography; Theoretical and/or physical chemistry

Toshiaki Kuramitsu, Sotaro Kusumoto, Hitomi Ohmagari, Miki Hasegawa, Pierre Thuéry, et al.. Coordinated halide and pseudo halide‐dependent structures and photoluminescence of defective double cubane Zn(II) clusters. European Journal of Inorganic Chemistry, In press, 2021 (12), pp.1160-1164. ⟨10.1002/ejic.202001138⟩. ⟨cea-03148306⟩