A new polytopic bis-diazacrown-ether-polypyridine ligand and its complexes with Zn(II) salts and mononuclear and dendritic Ru(II) precursors. Synthesis, absorption spectra, redox behavior, and luminescence properties

he new polytopic receptor 1 containing two terpyridine, one phenanthroline, and two diazacrown-ether sites has been prepared using a modular approach. Such a new species contains several pieces of information in its structure which can be processed by different metal ions to give different supramolecular inorganic architectures. Actually, reaction of 1 with Zn(CH3COO)(2) in methanol, and subsequent anion exchange, afforded the intramolecular ring-type [Zn(1)](2+) complex, which appears to be formed by a self-assembling reaction. A different synthetic approach, stepwise synthesis, allowed us to synthesize the two multicomponent compounds [(bpy)(2)Ru(mu -1)Ru(bpy)(2)](4+) (Ru2; bpy = 2,2'-bipyridine) and [{(bpy)(2)Ru(mu -2,3-dpp)}(2)Ru{(mu -2,3-dpp)Ru(bpy)(2)}(2)](12+) (Ru6; 2,3-dpp = 2,3-bis(2-pyridyl)pyrazine). The absorption spectra and luminescence properties of 1 and [Zn(l)](2+) are dominated by pi --> pi* transitions and excited states. The absorption spectra of the ruthenium compounds are dominated by ligand-centered (LC) bands in the UV region and metal-to-ligand charge-transfer (MLCT) bands in the visible. The latter compounds undergo several reversible metal-centered oxidations and ligand-centered reductions in the potential window investigated (-2,0/+2.0 V versus SCE) and exhibit MLCT luminescence in both acetonitrile fluid solution at room temperature and in butyronitrile rigid matrix at 77 K. Both the redox and photophysical properties of Ru2 and Ru6 can be assigned to specific subunits of the multicomponent structures. The data indicate that the {Ru(bpy)(2)}(2+) and the dendritic {Ru[(mu -2,3-dpp)Ru(bpy)(2)](2)}(6+) fragments appended to the polytopic 1 ligands behave as independent components of the multicomponent array