Self-Assembly, Structures, and Photophysical Properties of 4,4′-Bipyrazolate-Linked Metallo-Macrocycles with Dimetal Clips
Version 2 2008-03-17, 00:00
Version 1 2008-03-17, 00:00
dataset
posted on 2008-03-17, 00:00 authored by Qing-Fu Sun, Keith Man-Chung Wong, Li-Xia Liu, Hai-Ping Huang, Shu-Yan Yu, Vivian Wing-Wah Yam, Yi-Zhi Li, Yuan-Jiang Pan, Kai-Chao YuBy employing functional diimine ligands coordinated dipalladium(II,II) or diplatinum(II,II) clips as corners and the coplanar 4,4′-bipyrazolate dianion (L<sup>2−</sup>) ligand as linker, a series of bipyrazolate-bridged metallo-macrocycles, namely, [M<sub>8</sub>L<sub>4</sub>](NO<sub>3</sub>)<sub>8</sub> (M = Pd(dmbpy), <b>1</b>; Pd(bpy), <b>2</b>; Pt(bpy), <b>3a</b>; Pd(phen), <b>4</b>; Pt(phen), <b>5</b>; Pd(15-crown-5-phen), <b>6</b>; Pd(18-crown-6-phen), <b>8</b>; Pd(benzo-24-crown-8-phen), <b>10a</b>; Pt(15-crown-5-phen), <b>7a</b>, Pt(18-crown-6-phen), <b>9a</b>; Pt(benzo-24-crown-8-phen), <b>11a</b>) and [M<sub>6</sub>L<sub>3</sub>](NO<sub>3</sub>)<sub>6</sub> (M = Pt(bpy), <b>3b</b>; Pt(15-crown-5-phen), <b>7b</b>; Pt(18-crown-6-phen), <b>9b</b>; Pd(benzo-24-crown-8-phen), <b>10b</b>; Pt(benzo-24-crown-8-phen), <b>11b</b>), have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the 1<i>H</i>-bipyrazolyl ligands in aqueous solution. All these compounds have a crown-shaped cavity that can serve as host to solvent molecules and anions. The structures are characterized by elemental analysis, <sup>1</sup>H and <sup>13</sup>C NMR, ESI-MS, and in the cases of <b>1a</b> (the BF<sub>4</sub><sup>−</sup> salt of <b>1</b>), <b>2a</b> (the BF<sub>4</sub><sup>−</sup> salt of <b>2</b>), and <b>3b</b> by single-crystal X-ray diffraction analysis. Photophysical properties for complexes <b>1</b> and <b>2</b> are discussed.
