Coordinated Halide and Pseudo Halide‐Dependent Structures and Photoluminescence of Defective Double Cubane Zinc(II) Clusters

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<jats:title>Abstract</jats:title><jats:p>Tetranuclear zinc(II) complexes [Zn<jats:sub>4</jats:sub>(<jats:bold>L</jats:bold>)<jats:sub>4</jats:sub>(μ<jats:sub>3</jats:sub>‐OCH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>(X)<jats:sub>2</jats:sub>] (<jats:bold>L</jats:bold>=2‐((benzyloxy)carbonyl)‐6‐methoxyphenolate; X=Cl<jats:sup>−</jats:sup> (<jats:bold>1</jats:bold>), Br<jats:sup>−</jats:sup> (<jats:bold>2</jats:bold>), I<jats:sup>−</jats:sup> (<jats:bold>3</jats:bold>), N<jats:sub>3</jats:sub><jats:sup>−</jats:sup> (<jats:bold>4</jats:bold>), or NCS<jats:sup>−</jats:sup> (<jats:bold>5</jats:bold>)), have “defective” double‐cubane cores [Zn<jats:sub>4</jats:sub>O<jats:sub>6</jats:sub>], which are bridged by two μ<jats:sub>3</jats:sub>‐methoxo and four μ<jats:sub>2</jats:sub>‐phenolato oxygen atoms in each discrete complex. In halide complexes <jats:bold>1</jats:bold>, <jats:bold>2</jats:bold> and <jats:bold>3</jats:bold>, two zinc(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 zinc(II) in pseudo halide complexes <jats:bold>4</jats:bold> and <jats:bold>5</jats:bold> show slightly distorted octahedral geometries. The complexes exhibit blue fluorescence (λ<jats:sub>max</jats:sub>=415–428 nm) with high photoluminescence quantum yields (PLQY<jats:sub>S</jats:sub>, <jats:italic>Φ</jats:italic><jats:sub>em</jats:sub>) in the range of 0.22‐0.53 at room temperature in the solid state. Complex <jats:bold>5</jats:bold> has the highest <jats:italic>Φ</jats:italic><jats:sub>em</jats:sub> among the alkoxo‐bridged multinuclear zinc(II) clusters ever reported.</jats:p>

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