Designed Assembly and Structures and Photoluminescence of a New Class of Discrete ZnII Complexes of 1H-1,10-Phenanthroline-2-one

✍ Scribed by Jie-Peng Zhang; Yan-Yong Lin; Xiao-Chun Huang; Xiao-Ming Chen

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 177 KB
• Volume: 2006
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200600417

✦ Synopsis

Abstract

The hydrothermal reaction of 1__H__‐1,10‐phenanthroline‐2‐one (Hophen), zinc acetate, benzoic acid (Hba), and triethylamine (3.0 mL) yields the tetranuclear complex [Zn~4~(μ~3~‐OH)~2~(ophen)~4~(ba)~2~] (2), which features a chair‐like Zn~4~(μ~3~‐OH)~2~ cluster with two ba ligands centrosymmetrically oriented. [(OAc){Zn~3~(μ~3~‐OH)(ophen)~3~}(ox){Zn~3~(μ~3~‐OH)(ophen)~3~}(OAc)] (3; ox = oxalate) was isolated when less triethylamine (1.0 mL) was used. Two Zn~3~(μ~3~‐OH)(ophen)~3~ clusters in 3 are linked together by an oxalate to form a dumbbell‐like structure in which the acetate and oxalate ligands point outward from the Zn~3~(μ~3~‐OH)(ophen)~3~ cluster with an acute bending angle. A geometric analysis reveals that Zn~3~(μ~3~‐OH)(ophen)~3~ and dicarboxylate with an obtuse bending angle cannot form an infinite zigzag chain, whereas the ring isomer can. With isophthalate (ipa), thiophene‐2,5‐dicarboxylate (tda), and 4,4′‐oxybis(benzoate) (oba) instead of the acetate of 3 three new complexes, namely [{Zn~3~(μ~3~‐OH)(ophen)~3~}(ipa)~2~{Zn~3~(μ~3~‐OH)(ophen)~3~}]·0.5H~2~O (4), [{Zn~3~(μ~3~‐OH)(ophen)~3~}(tda)~2~{Zn~3~(μ~3~‐OH)(ophen)~3~}] (5), and [{Zn~3~(μ~3~‐OH)(ophen)~3~}(oba)~2~{Zn~3~(μ~3~‐OH)(ophen)~3~}] (6), were obtained in which two Zn~3~(μ~3~‐OH)(ophen)~3~ clusters are linked by a pair of ipa, tda, or oba ligands to form isostructural, cluster‐based 2:2 metallomacrocycles. Photoluminescence studies of 2–6 revealed that their luminescent properties are derived from ophen‐based π‐π* excited states. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)