Hexanuclear zinc(II) carboxylate complexes from the use of pyridine-2,6-dimethanol: Synthetic, structural and photoluminescence studies

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• 作者：Eugenia Katsoulakou^a ; Despina Dermitzaki^a ; Konstantis F. Konidaris^a ; Eleni E. Moushi^b ; Catherine P. Raptopoulou^c ; Vassilis Psycharis^c ; Anastasios J. Tasiopoulos^b ; Vlasoula Bekiari^d ; Evy Manessi-Zoupa^a ; Spyros P. Perlepes^a ; Theocharis C. Stamatatos^a ; ^e ; ^{tstamatatos@brocku.ca}
• 关键词：Crystal structures ; IR spectroscopy ; Metal carboxylates ; Photoluminescent zinc(II) complexes ; Polynuclear zinc(II) complexes ; Pyridine-2 ; 6-dimethanol
• 刊名：Polyhedron
• 出版年：2013
• 出版时间：22 March, 2013
• 年：2013
• 卷：52
• 期：Complete
• 页码：467-475
• 全文大小：719 K

文摘

The employment of pyridine-2,6-dimethanol (pdmH₂) in zinc(II) carboxylate chemistry is reported. The syntheses, crystal structures, and spectroscopic characterization are described for the structurally similar cluster compounds [Zn₆(OH)₂(O₂CR)₈(pdmH)₂] (R = Ph (1); Bu^t (2)), obtained in very good yields by the reactions between Zn(O₂CR)₂¡¤2H₂O (R = Ph, Bu^t) and pdmH₂ in a 3:1 molar ratio in MeOH or MeCN solvent media, respectively. The [Zn₆(¦Ì₃-OH)₂(¦Ì₃-OR)₂]⁸⁺ core of both clusters can be conveniently described as four edge-sharing triangles (RO^? = pdmH^?). The three crystallographically unique metal ions in both 1 and 2 are found in three different coordination environments (4-, 5- and 6-coordinate), within the same molecule, a very rare case in hexanuclear Zn(II) cluster chemistry. The benzoate-analogue Zn^II₆ (1) displays photoluminescence with a maximum at 404 nm, upon maximum excitation at 337 nm, whereas the pivalate-analogue Zn^II₆ (2) shows a non-emissive character; the origin of the photoluminescence is discussed.