The Synthesis, Structures And Properties Of Complexes Based On 1, 3, 5-tris (Triazol-1-ylmethyl)-2, 4, 6-trimethylbenzene Ligand

During the recent decades, functional coordination compounds rapidly become hot in the field of the inorganic chemistry. The reson is that the functional coordination compounds not only have remarkable architectures, but also their potential applications, including magnetism, adsorption and ion exchange, molecular recognition, etc., which makes people have great interest on the design and synthesis of these complexes. In this paper, a flexible tripodal ligand 1,3,5-tris (triazol-1-ylmethyl)-2,4,6- trimethylbenzene (TTTMB) with multiple coordinating sites and various spatial structures are selected as the main ligand to assemble such complexes, through the introduction of the different metal ion and secondary ligands. Then, we analyze the structures of these complexes and investigate their properties, respectively.This paper contains three parts as follows: 1. The octadecanuclear Ag macrocycle [Ag18(TTTMB)12](ClO4)18·30H2O 1'has been synthesized by the hydrothermal reaction of AgClO4, TTTMB and the second ligand.1'has the same framework with the reported complex [Ag18(TTTMB)12](NO3)18·30H2O 1. Take 1 for example, it has an infrequent cavum and unusual core arranged by Ag-Ag interactions within the complex. To our best knowledge, it is the maximum nuclearity in Ag macrocycles. In order to better study the photophysical properties of 1, we have obtained the trinuclear complex [Ag3(TTTMB)2]3+ 2 which can be deemed as the individual subunit of 1. We find that the photophysical properties of 2 are different from those of 1. So, we determine the unique properties of 1 derive from the macrocycle [Ag18(TTTMB)12]18+ rather than the trinuclear building unit [Ag3(TTTMB)2]3+. In this work, the solid-state luminescent properties of the octadecanuclear Ag macrocycle are carefully investigated. It is amazing that it shows the unique luminescent properties. That is to say, it displays the huge increased intensity of phosphorescence and the increased lifetime with decreasing temperature. Through the work of the photophysical properties investigated in the polar solution and MO calculations carried out, the origin of the solid-state luminescence in 1 has been suggested to be mainly derived from the 3LMMCT excited state, admixed with the 3IL excited state.2. By the simultaneous use of a tripodal ligand 1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (TTTMB) and adding second ligand, the complexes 3 [Cd4(1,2-bdc)4(TTTMB)4(H2O)4]n2nCl·4nCH3CN·6nH2O (2D),4 [Cd6(1,4-bdc)6(TTTMB)4(H2O)6]n·nH2O (2D),5 [Zn6(1,4-bdc)6(TTTMB)4(H2O)12]n·nH2O (1D),6 [Zn3(1,3-bdc)2 (TTTMB)2(μ2-SO4) (H2O)2]n·nH2O (2D) and 7 [Zn2(1,3-bdc)2 (TTTMB) (H2O)]n (2D)were obtained. The crystal structures of these complexes are confirmed by single-crystal X-ray diffraction. The luminescent properties of these complexes (3,4,5,6) are investigated.3. A tetranuclear Cu-contained compound 8 Na[Cu4 (TTTMB)2Br3]·Br4·1.5 H2C2O4 is obtained by the hydrothermal reaction of CuBr2, TTTMB and H2C2O4. Similarly, a tetranuclear Cu-contained compound 9 Na[Cu4 (TTTMB)2Cl3]·Cl4·1.5 H2C2O4 is obtained by the hydrothermal reaction of CuCl2, TTTMB and H2C2O4. It is very interesting that they have the same structures except for the bridging ligands. And they are novel in the complexes.