Issue 10, 1999

Blue luminescent zinc(II) complexes with polypyridylamine ligands: crystal structures and luminescence properties

Abstract

A series of blue luminescent zinc(II) complexes, [Zn(dpa)X2] [dpa = di-2-pyridylamine, X = OAc 1a, Cl 1b, CN 1c or 4-MeC6H4S 1d], [Zn(dpa)2][CF3SO3]2 2, [Zn(tpda)X2] [tpda = 2,6-bis(2-pyridylamino)pyridine, X = OAc 3a or Cl 3b] and [Zn(tpda)(CF3SO3)2] 4 has been prepared. Their molecular structures, except complex 4, have been established by X-ray crystallography. In the crystal lattice of 2 the [Zn(dpa)2]2+ cations and CF3SO3 anions are disposed in pairs via intermolecular hydrogen bonds [N(2)  · · ·  O(2) 2.865(4) Å]. The crystal packing of [Zn(dpa)(OAc)2] 1a revealed that two adjacent molecules associate in pairs through intermolecular hydrogen bonding [N(2)  · · ·  O(4′) 2.816(3) Å]. However, the crystal lattice of its tpda derivative 3a shows that the molecules are linked by extensive intermolecular hydrogen bonding between the amino groups and the acetate ligands [N(2)  · · ·  O(2′) 2.805(3) and N(4)  · · ·  O(4′) 2.860(3) Å] resulting in an interlocking hydrogen bond network. Polymeric one-dimensional tapes are generated through extended π–π stacking interactions between the molecules of [Zn(dpa)(4-MeC6H4S)2] 1d, and the thiolate groups are aligned in an all-anti conformation along the metal chain. In the case of [Zn(dpa)(CN)2] 1c, co-operative intermolecular hydrogen bonds and aromatic π–π interactions in its solid state lead to a supramolecular two-dimensional sheet. All the zinc(II) complexes display high energy intraligand 1(π–π*) fluorescence in degassed MeOH at 298 K, and intraligand 3(π–π*) phosphorescence in a glassy solution (MeOH–EtOH 1∶2 at 77 K). An emission band observed for 1c (418 nm) and 1d (481 nm) in their solid state emission spectra is ascribed to excimeric emission due to aromatic π–π interactions.

Supplementary files

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1999, 1581-1586

Blue luminescent zinc(II) complexes with polypyridylamine ligands: crystal structures and luminescence properties

K. Ho, W. Yu, K. Cheung and C. Che, J. Chem. Soc., Dalton Trans., 1999, 1581 DOI: 10.1039/A900504H

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