二十元环超大孔磷酸亚磷酸锌锰的合成与结构

本文以1,3-环己二甲胺[1,3-Cyclohexanebis(methylamine), CHBMA]为模板剂, 采用水热法合成了微孔磷酸亚磷酸锌锰 [H2CHBMA][Zn1.5Mn(HPO3)2(PO4)]·H2O(命名为TJPU-3Mn), 单晶结构解析显示该化合物为首个与超大孔磷酸铝JDF-20具有相同拓扑结构的微孔晶体, 沿c方向具有二十元环超大孔道, 孔道中的CHBMA分子均为顺式构象, 有望用于分离和识别CHBMA异构体.

Synthesis and Structure of Manganese Zinc Phosphate-phosphite with Extra Large Twenty-membered Ring Channels

A novel three-dimensional manganese zinc phosphatophosphite [H2CHBMA][Zn1.5Mn(HPO3)2(PO4)]·H2O(TJPU-3Mn) with extra-large twenty-membered ring channels was isolated by 1,3-cyclohexanebis(methylamine) as the template under hydrothermal conditions. Single crystal structure refinement reveals that TJPU-3Mn crystallizes in the monoclinic space group C2/c, with cell parameters, a=3.3929(7) nm, b=1.3045(3) nm, c=0.89713(18) nm, β=104.37(3)°, V=3.8465(13) nm3, Z=2. The connectivities of the ZnO4, MnO4, PO4 and HPO3 groups create a three-dimensional porous architecture with extra-large twenty-membered ring channels intersected by eight-membered rings. It is the first structure analogue to the famous aluminophsphate JDF-20. More interestingly, the diprotonated CHBMA cations in the channel are all in cis configuration, indicating the potential for separation and recognition of CHBMA isomers. Powder X-ray patterns reveal the structure of TJPU-3Mn sustains after the emission of water molecules obtained by calcining at 150 ℃ for 2 h.