Mao Feifei, Liu Jiadi, Hu Jinyu, Wu Hua
Department of Chemistry, Nanjing Agricultural University, Nanjing, 210095, P. R. China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the, Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, P. R. China.
Chem Asian J. 2020 Nov 2;15(21):3487-3493. doi: 10.1002/asia.202001002. Epub 2020 Sep 29.
Two mixed-metal zirconium iodates were prepared and studied as a case of chemical cosubstitution. The structure of Ag Zr(IO ) (P2 /c) features 0D [Zr(IO ) ] anion group and 1D [Ag(IO ) ] anionic chain, with the [Zr(IO ) ] anion groups interconnected by Ag ions into 3D network; LaZr(IO ) F (P2 /n) features 0D [Zr(IO ) F ] anion group and 2D [La(IO ) ] anionic layer, with the [Zr(IO ) F ] groups interlinked by La ions into 3D structure. Notably, LaZr(IO ) F is the first zirconium iodate fluoride reported. Wide optical band gaps of 3.77 and 4.13 eV are given for Ag Zr(IO ) and LaZr(IO ) F , respectively. Theoretical calculations confirmed that the weak d-d transition of Zr in the band structure leads to a moderate band gap of Ag Zr(IO ) , and the introduction of F into the zirconium iodate compound results in a large band gap of LaZr(IO ) F . Both of the compounds are birefringent materials with birefringences of 0.064 @1064 nm and 0.082 @1064 nm, respectively.
制备了两种混合金属碘酸锆并将其作为化学共取代的实例进行研究。AgZr(IO₆)₂（P2₁/c）的结构具有零维[Zr(IO₆)₂]阴离子基团和一维[Ag(IO₆)]阴离子链，[Zr(IO₆)₂]阴离子基团通过Ag离子相互连接形成三维网络；LaZr(IO₆)F（P2₁/n）具有零维[Zr(IO₆)F]阴离子基团和二维[La(IO₆)]阴离子层，[Zr(IO₆)F]基团通过La离子相互连接形成三维结构。值得注意的是，LaZr(IO₆)F是报道的首例碘酸锆氟化物。AgZr(IO₆)₂和LaZr(IO₆)F的宽带隙分别为3.77和4.13 eV。理论计算证实，能带结构中Zr的弱d-d跃迁导致AgZr(IO₆)₂具有适中的带隙，而在碘酸锆化合物中引入F导致LaZr(IO₆)F具有较大的带隙。这两种化合物都是双折射材料，在1064 nm处的双折射分别为0.064和0.082。
