Assembly and photocatalysis of three novel metal–organic frameworks tuned by metal polymeric motifs

<div><p></p><p>By using a thiodiacetate, phenanthroline and tuning the metal salts in the reaction system, three new metal-organic coordination complexes, {[Co(MOPIP)<sub>2</sub>(tda)]·H<sub>2</sub>O}<sub>1∕2</sub> (<b>1</b>), [Cd(MOPIP)<sub>2</sub>(tda)]<sub>2</sub>·3H<sub>2</sub>O (<b>2</b>) and [Cu<sub>5</sub>I<sub>4</sub>(MOPIP)<sub>3</sub>·H<sub>2</sub>O]<sub>n</sub> (<b>3</b>) (tda = S(CH<sub>2</sub>COO)<sub>2</sub><sup>2−</sup>, thiodiacetate; MOPIP = 2-(4-methoxyphenyl)-1<i>H</i>-imidazo[4,5-<i>f</i>][1,10]phenanthroline), have been prepared through hydrothermal reactions. In <b>1</b> and <b>2</b>, the metal (Co<sup>2+</sup>/Cd<sup>2+</sup>) centers are connected by tda to form a mononuclear molecule, which connect to a two-dimensional (2D) layer by N-H···O hydrogen bonds. By selecting the copper iodide salt we get <b>3</b>, where the Cu<sup>+</sup> center exhibits three different coordination types, which has never been seen before in the same compound, and linked by iodide and MOPIP to construct a new 3D framework. <b>3</b> represents the first example of MOPIP showing a new coordination mode with four nitrogens all coordinated. The metal salts play an important role in assembly of the structures of <b>1</b>-<b>3</b>. Introduction of MOPIP shows significant effect on the dimensionalities of complexes. The fluorescence and catalytic properties of <b>1</b> and <b>3</b> have also been investigated.</p></div>