| Summary: | The self-assembly of 2,6-diformyl-4-methylphenol (<b>DFMP</b>) and 1-amino-2-propanol (<b>AP</b>)/2-amino-1,3-propanediol (<b>APD</b>) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H<sub>3</sub>L and H<sub>5</sub>L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu<sub>4</sub>(HL<sup>2−</sup>)<sub>2</sub>(N<sub>3</sub>)<sub>4</sub>]·4CH<sub>3</sub>OH·56H<sub>2</sub>O (<b>1</b>) and [Cu<sub>4</sub>(L<sup>3−</sup>)<sub>2</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>), dinuclear [Cu<sub>2</sub>(H<sub>3</sub>L1<sup>2−</sup>)(N<sub>3</sub>)(H<sub>2</sub>O)(NO<sub>3</sub>)] (<b>3</b>), polynuclear {[Cu<sub>2</sub>(H<sub>3</sub>L1<sup>2−</sup>)(H<sub>2</sub>O)(BF<sub>4</sub>)(N<sub>3</sub>)]·H<sub>2</sub>O}<sub>n</sub> (<b>4</b>), heptanuclear [Cu<sub>7</sub>(H<sub>3</sub>L1<sup>2−</sup>)<sub>2</sub>(O)<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>6</sub>]·6CH<sub>3</sub>OH·44H<sub>2</sub>O (<b>5</b>), and decanuclear [Cu<sub>10</sub>(H<sub>3</sub>L1<sup>2−</sup>)<sub>4</sub>(O)<sub>2</sub>(OH)<b><sub>2</sub></b>(C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>4</sub>] (C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>2</sub>·20H<sub>2</sub>O (<b>6</b>). X-ray studies have revealed that the basic building block in <b>1</b>, <b>3</b>, and <b>4</b> is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL<sup>2−</sup> or H<sub>3</sub>L1<sup>2−</sup>, and one μ-1,1-azido (N<sub>3</sub><sup>−</sup>) ion and in <b>2</b>, <b>5</b>, and <b>6</b> by μ-phenoxide oxygen of L<sup>3−</sup> or H<sub>3</sub>L1<sup>2−</sup> and μ-O<sup>2−</sup> or μ<sub>3</sub>-O<sup>2−</sup> ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (<b>1</b> and <b>6</b>), 2D-sheets (<b>3</b>), and 3D-structures (<b>4</b>). In <b>5</b>, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In <b>1</b>, <b>3</b>, and <b>5,</b> Cu(II) ions in [Cu<sub>2</sub>] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm<sup>−1</sup>.
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