A Systematic Research
on the Synthesis, Structures,
and Application in Photocatalysis of Cluster-Based Coordination Complexes
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Abstract
To
search for effective photocatalysts in the field of cluster-based
coordination complexes, we synthesized {[Cd<sub>2</sub>(dcpp)(beb)<sub>2</sub> (H<sub>2</sub>O)]·H<sub>2</sub>O}<sub><i>n</i></sub> (<b>1</b>), [Cd<sub>2</sub>(dcpp)(bmb)(H<sub>2</sub>O)<sub>2</sub>]<sub><i>n</i></sub> (<b>2</b>), {[Cd<sub>2</sub>(dcpp)(2,2′-bipy)(H<sub>2</sub>O)<sub>2</sub>]·2H<sub>2</sub>O}<sub><i>n</i></sub> (<b>3</b>), and {[Cd<sub>2</sub>(dcpp)(4,4′-bipy)<sub>0.5</sub>(H<sub>2</sub>O)<sub>3</sub>]·H<sub>2</sub>O}<sub><i>n</i></sub> (<b>4</b>) by utilizing a butterfly-shaped
multidentate carboxylic acid (4,5-di(4′-carboxylphenyl)phthalic
acid) (H<sub>4</sub>dcpp)) and N-donor ligands (1,4-bis(2-ethylbenzimidazol-1-ylmethyl)
benzene (beb), 1,4-bis(2-methylbenzimidazol-1-ylmethyl)
benzene (bmb), 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine
(4,4′-bipy)). Complexes <b>1</b>–<b>4</b> are constructed based on different SBUs. Complexes <b>1</b> and <b>2</b> possess three-dimensional (3D) pillar-layered
frameworks based on noncluster-type SBUs and dinuclear Cd<sub>2</sub> clusters units, respectively. Complex <b>3</b> is a 3D porous
structure building on Cd<sub>4</sub> clusters SBUs. Complex <b>4</b> is constructed from rare infinite botryoid-like Cd cluster
chains and exhibits a 3D complicated framework. The research on optical
energy gaps of complexes <b>1</b>–<b>4</b> indicates
that these complexes are potential semiconductive materials. Moreover,
complexes <b>1</b>–<b>4</b> are applied to catalyze
the reaction of photocatalytic degradation of methylene orange (MO)
under high-pressure mercury lamp irradiation. Excitingly, they exhibit
good photocatalytic properties in the presence of H<sub>2</sub>O<sub>2</sub>, and the degradation rates for <b>1</b>–<b>4</b> increase from 43% (without photocatalyst) to 97, 78, 85,
and 67%, respectively, after 100 min of irradiation. The photoluminescent
properties of complexes <b>1</b>–<b>4</b> were
also studied