title: Towards a new family of photoluminescent organozinc 8-hydroxyquinolinates with a high propensity to form noncovalent porous materials.
abstract: We report on investigations of reactions of tBu(2)Zn with 8-hydroxyquinoline (q-H) and the influence of water on the composition and structure of the final product. A new synthetic approach to photoluminescent zinc complexes with quinolinate ligands was developed that allowed the isolation of a series of structurally diverse and novel alkylzinc 8-hydroxyquinolate complexes: the trinuclear alkylzinc aggregate [tBuZn(q)](3) (1(3)), the pentanuclear oxo cluster [(tBu)(3)Zn(5)(μ(4) -O)(q)(5)] (2), and the tetranuclear hydroxo cluster [Zn(q)(2)](2)[tBuZn(OH)](2) (3). All compounds were characterized in solution by (1)H NMR, IR, UV/Vis, and photoluminescence (PL) spectroscopy, and in the solid state by X-ray diffraction, TGA, and PL studies. Density functional theory calculations were also carried out for these new Zn(II) complexes to rationalize their luminescence behavior. A detailed analysis of the supramolecular structures of 2 and 3 shows that the unique shape of the corresponding single molecules leads to the formation of extended 3D networks with 1D open channels. Varying the stoichiometry, shape, and supramolecular structure of the resulting complexes leads to changes in their spectroscopic properties. The close-packed crystal structure of 1(3) shows a redshifted emission maximum in comparison to the porous crystal structure of 2 and the THF-solvated structure of 3.
authors.affiliation: Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland.
authors.forename: Kamil
authors.initials: K
authors.lastname: Sokołowski
authors.forename: Iwona
authors.initials: I
authors.lastname: Justyniak
authors.forename: Witold
authors.initials: W
authors.lastname: Sliwiński
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Sołtys
authors.forename: Adam
authors.initials: A
authors.lastname: Tulewicz
authors.forename: Arkadiusz
authors.initials: A
authors.lastname: Kornowicz
authors.forename: Robert
authors.initials: R
authors.lastname: Moszyński
authors.forename: Janusz
authors.initials: J
authors.lastname: Lipkowski
authors.forename: Janusz
authors.initials: J
authors.lastname: Lewiński