含二硒磷酸配位基與含氮配位基之鋅金屬錯合物之研究

Research of Zinc Complexes Containing Dialkyl Diselenophosphate Ligands and 4, 4’-bipydrine ligand

蔡坤峯(Kun-Feng Tsai)

指導教授 ： 楊千金

中原大學/理學院/化學系/碩士(2006年)

https://doi.org/10.6840/cycu200600677

摘要

本次實驗利用二硒磷酸配位基NH4Se2P(OR)2 (dialkyl diselenopho- sphate ligand) (R= Et, nPr, iPr)與過氯酸鋅(Zn(ClO4)2‧6H2O)以及雙吡啶環(4,4’-bipypridine)以4：2：1與2：2：1不同的莫耳比不同溶劑下進行反應，發現有兩種不同的化合物，比較它們在光譜上與晶體結構上的差異。

NH4Se2P(OR)2 (dialkyl diselenophosphate ligand) (R=Et, nPr, iPr)與過氯酸鋅(Zn(ClO4)2‧6H2O)以及雙吡啶環(4,4’-bipypridine)以4：2：1在丙酮中室溫下進行反應，可得到自組合而成的[{Zn(Se2P(OR)2)2}2 (N(C5H4)2N)]雙金屬配位化合物。

NH4Se2P(OR)2 (dialkyl diselenophosphate ligand) (R= Et, nPr, iPr)與過氯酸鋅(Zn(ClO4)2‧6H2O)以及雙吡啶環(4,4’-bipypridine)以2：2：1在甲醇中室溫下進行反應，可得到自組合而成的[{Zn(Se2P(OR)2)2}2 (N(C5H4)2N)]鏈狀配位聚合物。

由同樣的藥品，以不同比例與不同溶劑可得到不同自組合所形成的化合物，化合物的鑑定由元素分析、核磁共振儀、基質輔助雷射脫附游離質譜儀與單晶X-ray繞射儀所鑑定。

關鍵字

含氮配位基 ； 二硒磷酸

並列摘要

Complexes [{Zn(Se2P(OR)2)2}2(N(C5H4)2N)] (R= Et, nPr, iPr) were prepared from the reaction of NH4Se2P(OR)2, Zn(ClO4)2‧6H2O and 4,4’-bipypridine (N(C5H4)2N) in a molar ratio of 4: 2: 1 in acetone at room-temperature and stirred for two hours. The complexes were characterized by elemental analysis, 1H, 31P, 77Se NMR, positive MALDI-TOF mass and X-ray. The structure of [{Zn(Se2P(OR)2)2}2 (N(C5H4)2N)] consists of 4,4’-bipypridine as a bridge to connect two [Zn(dsep)2] units. One of the dialkyl diselenophosphate ligands had changed the coordination pattern from chelating in [Zn(dsep)2] to dangling in the title compounds. The complexes formed by [Zn(dsep)2] and 4,4’-bipypridine were called binuclear coordination compounds. The coordination geometry around the zinc atom is distorted tetrahedral.

Complexes [{Zn(Se2P(OR)2)2}(N(C5H4)2N)]n (R= Et, iPr) were prepared from the reaction of NH4Se2P(OR)2, Zn(ClO4)2‧6H2O and 4,4’-bipypridine (N(C5H4)2N) in a molar ratio of 2: 2: 1 in methanol at room-temperature and stirred for 5 minutes. Both complexes were characterized by elemental analysis, 1H, 31P, 77Se NMR, positive MALDI-TOF mass and X-ray. While the structure of [{Zn(Se2P (OEt)2)2}(N(C5H4)2N)]n was polymeric zigzag chain, the structure of [{Zn(Se2P(OiPr)2)2}(N(C5H4)2N)]n was straight-chain topology(crossover by layers). These two coordination polymers displayed orange luminescence at 77K.

並列關鍵字

dsep ； bipydrine

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