Synthesis of a Single Four-Ring (S4R) Molecular Zinc Phosphate and Its Assembly to an Extended Polymeric Structure: A Single-Crystal and in-Situ MAS NMR Investigation
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- 作者：Srinivasan Natarajan ; Leo van Wü ; llen ; Wilhelm Klein ; and Martin Jansen
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：October 6, 2003
- 年：2003
- 卷：42
- 期：20
- 页码：6265 - 6273
- 全文大小：184K
- 年卷期：v.42,no.20(October 6, 2003)
- ISSN：1520-510X
文摘
A reaction of ZnO, HCl, H3PO4, and 2-pyridylpiperazine in THF/H2O mixture at 75 
C for 72 h produces a new zincphosphate, [(C5NH5)(C4N2H10)][Zn(H2PO4)2(HPO4)], I. Zinc phosphate I consists of single four-ring (S4R) units withterminal phosphoryl groups hanging from the Zn center. On reaction with zinc acetate dihydrate in the presenceof water at 100 C, I gave another new zinc phosphate, [(C5NH5)(C4N2H10)][Zn2(H2PO4)(HPO4)(PO4)]·2H2O, II. IIhas a layer structure with apertures formed by 4- and 8-T atoms (T = Zn, P). An examination of the two structuresreveals that I and II are related, II being formed by the direct addition of Zn2+ ions to I. Room-temperature 31P MASNMR studies show the presence of different phosphorus species in both compounds. An in-situ 31P MAS NMRinvestigation on the formation of II from I in the presence of Zn2+ ions and water reveals the transformation to befacile. What is noteworthy in this study is that the structural integrity of the S4Rs has been maintained during theformation of II. Donor-acceptor hydrogen bond interactions and 
pi.gif" BORDER=0 >-pi.gif" BORDER=0 > interactions involving the pyridyl groups alsoappear to play subtle roles in both phosphates. This study, the first attempt of its kind, combines the principles ofsupramolecular organic chemistry with inorganic building units and contributes to our understanding of the formationof framework solids.
C for 72 h produces a new zincphosphate, [(C5NH5)(C4N2H10)][Zn(H2PO4)2(HPO4)], I. Zinc phosphate I consists of single four-ring (S4R) units withterminal phosphoryl groups hanging from the Zn center. On reaction with zinc acetate dihydrate in the presenceof water at 100 C, I gave another new zinc phosphate, [(C5NH5)(C4N2H10)][Zn2(H2PO4)(HPO4)(PO4)]·2H2O, II. IIhas a layer structure with apertures formed by 4- and 8-T atoms (T = Zn, P). An examination of the two structuresreveals that I and II are related, II being formed by the direct addition of Zn2+ ions to I. Room-temperature 31P MASNMR studies show the presence of different phosphorus species in both compounds. An in-situ 31P MAS NMRinvestigation on the formation of II from I in the presence of Zn2+ ions and water reveals the transformation to befacile. What is noteworthy in this study is that the structural integrity of the S4Rs has been maintained during theformation of II. Donor-acceptor hydrogen bond interactions and pi.gif" BORDER=0 >-pi.gif" BORDER=0 > interactions involving the pyridyl groups alsoappear to play subtle roles in both phosphates. This study, the first attempt of its kind, combines the principles ofsupramolecular organic chemistry with inorganic building units and contributes to our understanding of the formationof framework solids.