The Syntheses, Structures And Properties Of Coinage Metal Complexes With Pyrazolates And Bipyrazolates

In this paper, we designed and synthesized five organic ligands, containing two pyrazolates and three semi-rigid bipyrazolates. 17 complexes based on these ligands have been synthesized successfully, which were characterized by 1H NMR, elemental analyses, IR spectroscopy, single-crystal X-ray diffraction and power X-ray diffraction, moreover, their thermal stability and fluorescent property were also studied.The five organic ligands are as follows: 4-acetoxy-3,5-diphenyl-1H-pyrazole(HL1) 4-allyl-3,5-diphenyl-1H-pyrazole(HL2) 2,5-bis[(3′5′-diphenyl-1H-4′-yl)-methylene]furan(H2L1) 2,5-bis[(3′5′-dimethyl-1H-4′-yl)-methylene]thiophene(H2L2) 2,5-bis[(3′5′-diphenyl-1H-4′-yl)-methylene]thiophene(H2L3)The 17 complexes and their abbreviations: [Cu(OAc Ph2Pz)]3(1) [AuⅠ(OAc Ph2Pz)]3(2) [AuⅢCl2(OAc Ph2Pz)]3(3) [AuⅠ(C3H5Ph2Pz)]3(4) [AuⅠ2AuⅢCl2(C3H5Ph2Pz)3](5) [AuⅠAuⅢ2Cl4(IPh2Pz)3](6) [AuⅢCl2(C3H5Ph2Pz)]3(7) [AuⅢCl2(Cl Ph2Pz)]3(8) [AuⅢCl2(IPh2Pz)]3(9) [Au(Me Ph2Pz)]3(10) [Me Ph2 Pz H2]+[Au Cl4]-(11) [Ag2(H2L1)2](CF3SO3)2(12) [Cu2(H2L1)2]Cl4(13) [Cu2(H2L2)2]Br4(14) [Cu2(H2L3)2]Cl4(15) [Cu6L33] ?THF(16) [Ag6L33] ?THF(17)The 17 complexes are classified into three categeries according to the ligands:1. Cyclic trinuclear complex: Complex 1–10. The pyrazoles can become bidentate ligands under base environment and tend to coordinate linearly with two-coordinate CuI or AuI sites to form cyclic trinuclear structures. Trinuclear AuⅢ3 pyrazolato complexes and mixed-valent complexes were prepared by oxidation of trinuclear AuI with the new oxidant iodinemonochloride.2. Dinuclear complex: the twisted rectangular complex 14 looks somehow like the figure of “8” shape, the small size of the 3,5-substituent(methyl) and the lack of π···π interaction result in the formation of thus structure; 12, 13, 15 are all M2L2 rectangular, and the ligands are in the undeprotonated form.3. Hexanuclear complex: Complex 16 and 17 exhibit a hexanuclear trigonal prismatic cage, synthesized by the semi-rigid bipyrazolyl ligand 2,5-bis(4′-methylene-1H-3′,5′-diphenylpyrazole)thiophene with copper(I) and silver(I), two parallel M3N6 subunits are in frontal mode and approximately parallel arranged, the thiophene rings and the nine-membered M3N6 rings are close to vertical. The observed trigonal prismatic cage is actually a natural result of the self-assembly of these components. The crystal structure of complex 16 in combination with elemental analyses, thermal analyses clearly shows that a THF molecule is sandwiched between the two Cu3Pz3 subunits. Comparison was made to compare the relevant distances and volumes of relevant M6L3 cages, trying to get more valuable information to guide the design and synthesis of the ligand and complex.The main result of my research work can be summarized into the following two points:1. A novel oxidant—ICl that can be applied to the cyclic trinuclear gold(I) pyrazolate complexes was been found, compared with reported oxidant aqua regia and chlorine, ICl has the advantages of simple operation and tends to form trinuclear AuⅢ3 pyrazolato complexes.2. The size of spacer has great effect on the height and volume of the trigonal prismatic cage, alter the spacer can adjust the size of the cage.