Series of Lead Oxide Hydroxide Nitrates Obtained by Adjusting the pH Values of the Reaction Systems

A series of lead(II) nitrates have been synthesized by a hydrothermal method and adjusting the pH values of the reaction systems. Pb20O6(OH)16(NO3)12 and Pb2O(OH)NO3, crystallize in the centrosymmetric space group P1̅ and Pbca, respectively. The structure of Pb20O6(OH)16(NO3)12 features infinite cationic chains of [Pb20O6(OH)16]∞ running along c axis, and the nitrate groups as the counterions reside between adjacent chains, while the structure of Pb2O(OH)NO3 can be described as alternate stacking of cationic [Pb2O(OH)]∞ layers with anionic [NO3](-) layers along [001] direction by the weak Pb-O bonds, forming a 3D framework with 1D tunnels of 12-member rings (MRs). [Pb4(OH)4](NO3)4, crystallizing in the noncentrosymmetric space group Cc, has been studied as the nonlinear optical material for the first time. The second harmonic generation (SHG) measurement indicates that the SHG responses of [Pb4(OH)4](NO3)4 are 0.7 times that of KDP. Theoretical calculations confirmed the SHG efficiency of [Pb4(OH)4](NO3)4 originates from the cooperative effect of NO3(-) groups and lead oxygen polyhedras in the structure. Meanwhile, the relationship between pH value and ratio of Pb/OH(-) in the molecules presents a positive correlation, which results in the diversity of these structures under different pH value.