Chen Peng, Li Jiyang, Duan Fangzheng, Yu Jihong, Xu Ruren, Sharma Raj Pal
State Key Lab of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, PR China.
Inorg Chem. 2007 Aug 6;46(16):6683-7. doi: 10.1021/ic062103+. Epub 2007 Jul 11.
Three new chloride-rich zincophosphates including two zero-dimensional (0D) clusters [dl-Co(en)3]2[Zn4(H2PO4)2(HPO4)2Cl8] (denoted ZnPO-CJ33) and [d-Co(en)3]2[Zn4(H2PO4)2(HPO4)2Cl8] (denoted ZnPO-CJ34), and one-dimensional (1D) zincophosphate chain [dl-Co(en)3][Zn2(H2PO4)(HPO4)2Cl2] (denoted ZnPO-CJ35) have been solvothermally prepared. ZnPO-CJ33 and ZnPO-CJ34 possess the same cluster structure as the macroanionic [Zn4H6P4O16Cl8]6- unit formed by alternation of ZnOCl3/ZnO3Cl and HPO4/H2PO4 tetrahedra but differ in the countercations. The racemic [dl-Co(en)3]3+ cations are located among the clusters of ZnPO-CJ33, whereas chiral [d-Co(en)3]3+ cations are located among the clusters of ZnPO-CJ34. ZnPO-CJ34 templated by the optically pure chiral [d-Co(en)3]3+ cations is the first chiral monomeric zincophosphate. ZnPO-CJ35 templated by the racemic [dl-Co(en)3]3+ cations possesses a 1D infinite chain structure formed by the alternation of ZnO3Cl and HPO4/H2PO4 tetrahedra. The 1D chain structure of ZnPO-CJ35 can also be viewed as generated from the condensation of 0D clusters of ZnPO-CJ33, with the terminal Cl ions replaced by HPO4 groups. Experimentally, the structural transformation from ZnPO-CJ33 to ZnPO-CJ35 has been investigated.
通过溶剂热法制备了三种新型富氯磷酸锌，包括两个零维（0D）簇合物[dl-Co(en)3]2[Zn4(H2PO4)2(HPO4)2Cl8]（记为ZnPO-CJ33）和[d-Co(en)3]2[Zn4(H2PO4)2(HPO4)2Cl8]（记为ZnPO-CJ34），以及一维（1D）磷酸锌链[dl-Co(en)3][Zn2(H2PO4)(HPO4)2Cl2]（记为ZnPO-CJ35）。ZnPO-CJ33和ZnPO-CJ34具有与由ZnOCl3/ZnO3Cl和HPO4/H2PO4四面体交替形成的大阴离子[Zn4H6P4O16Cl8]6-单元相同的簇结构，但抗衡阳离子不同。外消旋的[dl-Co(en)3]3+阳离子位于ZnPO-CJ33的簇之间，而手性的[d-Co(en)3]3+阳离子位于ZnPO-CJ34的簇之间。由光学纯手性[d-Co(en)3]3+阳离子模板化的ZnPO-CJ34是第一个手性单体磷酸锌。由外消旋旋的[dl-Co(en)3]3+阳离子模板化的ZnPO-CJ35具有由ZnO3Cl和HPO4/H2PO4四面体交替形成的一维无限链结构。ZnPO-CJ35的一维链结构也可以看作是由ZnPO-CJ33的零维簇缩合产生的，末端的Cl离子被HPO4基团取代。实验上，研究了从ZnPO-CJ33到ZnPO-CJ35的结构转变。
