Reactivities Of Trnasition Metal And Tetrapyrazolyl-based Ligand

The coordination polymers derived from Cu(I) halides (Cl, Br, I) or pseudohalides (CN, SCN) and organic ligands have received much attention currently not only because of their structural diversities but also their potential applications as optical, adsorbent, and catalytic materials. Most of the architectures reported to date are based upon a family of mono-, di- or tri- pyrazolyl-based ligands while only Reger focused on the use of tetrapyrazolyl-based ligands. In this thesis, we deliberately chose two kinds of tetrapyrazolyl-based ligands and carried out their reactions with Cu(I)X (X = Cl, Br, I, SCN, CN) at solvothermal conditions. 9 Cu(I) complexes were got.1. Solvothermal reactions of Cu(I)X (X = Cl, Br, I, SCN, CN) and 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazole)propane (tdmpp) ligands afforded 5 new [CunXn]-based (X = Cl,Br,I, SCN, CN) coordination polymers. The 3D framework of bulk CuX (X = Cl,Br,I, SCN, CN) was cracked by the ligands into various [CunXn] motifs, such as dimeric [Cu₂(μ-X)₂] in [{Cu₂Cl₂(tdmpp)}·0.5MeCN]_n (1) ,[{Cu₂Br₂(tdmpp)}·0.5MeCN]_n (2),[{Cu₂I 2(tdmpp)}·MeCN]_n (3) and [{Cu₂(SCN)2(tdmpp)}]_n (4); 1D chain fragment in [Cu₃(CN)3(tdmpp)]_n (5). The photoluminescent properties of them were studied. It is noted that the emission maxima of 1-5 are red-shifted compared to that of tdmpp , which may be due to the electron-withdrawing properties of halides and pseudohalides. Compounds 1, 2, 3, 4 and 5 exhibit a gradually blue-shifted emission band.2. Solvothermal reactions of Cu(I)X (X = Cl , Br , I, CN) and 1,1,3,3-tetrakis(1-pyrazole)propane (tpp) ligands afforded 4 new [CunXn]-based (X = Cl,Br,I, CN) coordination polymers. The 3D framework of bulk CuX (X = Cl,Br,I, CN) was cracked by the ligands into various [CunXn] motifs, such as dimeric [Cu₂X₂] in Cu₄Cl₄(tpp) (6),Cu₄Br₄(tpp) (7); dimeric [Cu₂(μ-X)₂] and tetrametric [Cu₂(μ-I)₄] in [{Cu₃I₃(tpp)₂}·MeCN]_n (8); 1D chain fragment in [Cu₄(CN)₄(tpp)·MeCN]_n (9). The photoluminescent properties of them were studied. It is noted that the emission maxima of 1-4 are red-shifted compared to that of tdmpp, which may be due to the electron-withdrawing properties of halides and pseudohalides. Compounds 6, 7, 8 and 9 exhibit a gradually blue-shifted emission band.