Zhang Rong-Hua, Xia Wen-Sheng, Wang Hong-Xin, Zhou Zhao-Hui
College of Chemistry and Chemical Engineering, State Key Laboratory of Physical Chemistry of Solid Surface, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, Xiamen University, Xiamen 361005, China.
Inorg Chem Commun. 2009 Jun 1;12(6):583-587. doi: 10.1016/j.inoche.2009.04.028. Epub 2009 May 7.
Adduct of mononuclear and dinuclear citrate zinc complex [Zn(Hcit)(phen)(HO)][Zn(Hcit)(phen)(HO)]·13.5HO () and its aggregate [Zn(Hcit)(phen)]·14nHO () (Hcit = citric acid, phen = 1,10-phenanthroline) were synthesized in weak acidic solutions. The former was obtained from the reaction of zinc nitrate, citric acid and phenanthroline in a molar ratio of 3 : 2 : 3, while a slightly excess of phenanthroline results in the formation of the polymeric product in a molar ratio of 3 : 2 : 4. Transformation of to was finished by the reaction of with an equimolar of phenanthroline in 72% yield. Reverse conversion of to is obtained in 77% yield, showing an equilibrium between and . Neutral compound consists of one monomeric anionic unit [Zn(Hcit)(phen)(HO)] and one dimeric cationic unit [Zn(Hcit)(phen)(HO)] that connect each other by strong hydrogen bonds [O6⋯O4w 2.636(2); O7⋯O3w 2.630(3) Å]. In , the citrate ligand links each trinuclear unit [Zn(Hcit)(phen)] to generate an infinite 1D chain that extents into a 3D supramolecular structure by intra- and inter-molecular hydrogen bonds. Moreover, and exhibit strong fluorescence at room temperature.
单核和双核柠檬酸锌配合物[Zn(Hcit)(phen)(H₂O)][Zn(Hcit)(phen)(H₂O)]·13.5H₂O（）及其聚集体[Zn(Hcit)(phen)]·14nH₂O（）（Hcit = 柠檬酸，phen = 1,10 - 菲咯啉）在弱酸性溶液中合成。前者由硝酸锌、柠檬酸和菲咯啉以3 : 2 : 3的摩尔比反应得到，而稍微过量的菲咯啉会导致以3 : 2 : 4的摩尔比形成聚合物产物。通过与等摩尔的菲咯啉反应，以72%的产率完成了向的转化。向的逆转化产率为77%，表明和之间存在平衡。中性化合物由一个单体阴离子单元[Zn(Hcit)(phen)(H₂O)]和一个二聚阳离子单元[Zn(Hcit)(phen)(H₂O)]组成，它们通过强氢键[O6⋯O4w 2.636(2); O7⋯O3w 2.630(3) Å]相互连接。在中，柠檬酸配体连接每个三核单元[Zn(Hcit)(phen)]以生成无限的一维链，该链通过分子内和分子间氢键扩展成三维超分子结构。此外，和在室温下表现出强荧光。
