| Perovskite complexes have attracted much attention in the optical field due to their excellent properties such as adjustable band gap and long carrier diffusion length.Photocatalytic reaction is considered as an important way to develop green energy and control greenhouse gases,which also makes perovskite complexes become potential materials of photocatalysis.The addition of rare earth metals can further enrich the optical properties of the complex,so that it has potential in the application of luminescence.Meanwhile,novel single-ion magnets with unique properties can be synthesized by using kramers metal ions as spin centers.The main work of this paper includes the design and synthesis of two transition metal perovskite complexes obtained by the reaction of 2,2'-bipyridine(2,2'-bpy)with transition metals Ru IIIand Zn II,and the microcrystalline and nanocrystalline materials of the complexes are applied to the field of photocatalysis.Meanwhile,three rare earth lead iodine perovskite complexes were synthesized by the reaction of bis(diphenylphosphino)methane dioxide(dppm O2)with rare earth ions La III,Tb IIIand Nd III,and were characterized in structures and properties.In addition,three mononuclear lanthanide complexes were gained by the reaction of1,2-bis(diphenylphosphino)benzene dioxide(dppb O2)with Kramers ions Ce III,Sm IIIand Yb III,and studied in crystal structure as well as magnetic properties.The main content includes the following four parts:In chapter 1,the content is the introduction,which mainly includes the development of perovskite and its application in photocatalysis,also single molecule magnets(SMMs),single ion magnets(SIMs)and the topic selection basis and research results of this paper.In chapter 2,Two complexes were synthesized by using 2,2'-bipyridine ligand(2,2'-bpy)and transition metal ions Ru IIIand Zn IIrespectively.Meanwhile,Pb Xnchain(X=I)was introduced as the anionic part to obtain two kinds of lead iodine perovskite complexes[Ru(2,2'-bpy)3][Pb2.75I7.5](1)and[Zn(2,2'-bpy)3][Pb2.75I7.5](2).Their crystal structure and optical properties were characterized to explore the effect of photocatalytic hydrogen evolution.The complexes 1 and 2 were prepared into nanocrystalline materials by ligand-assisted reprecipitation method and researched on their crystal structure and optical properties.Compared with microcrystalline materials,the performance and reaction mechanism of photocatalytic HER of the two materials under different crystal size,material dose and p H were investigated.In chapter 3,we designed and synthesized rare earth lead iodine complexes obtained by the reaction of bis(diphenylphosphino)methane dioxide(dppm O2)with rare earth metal ions La III,Tb IIIand Nd III,with molecular formulas of[La(dppm O2)4][Pb5I13](3),[Tb(dppm O2)3][Pb5.5I14](4)and[Nd(dppm O2)4][Pb2.5I8](5).The crystallographic test and performance characterization reveal that they all have novel spatial structures,which caused by the combination of different rare earth ions as metal centers.In chapter 4,[Ce(dppb O2)2Cl3]·THF(6)?[Sm(dppb O2)2Cl3]·THF(7)and[Yb(dppb O2)2Cl2]Cl·(H2O)2THF(8)were designed and synthesized with ligand1,2-bis(diphenylphosphino)benzene dioxide(dppb O2)and Kramers ions Ce III,Sm III,Yb III.The crystal structure characterization shows that complexes 6 and 7 are isostructural seven-coordinate with distorted geometries,while complex 8 is six-coordinate with an octahedron geometry.Dynamic magnetic property measurements indicate their field induced slow magnetic relaxation behaviours. |
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