Studies On Construction, Photochemical And Photophysical Properties Of Complexes From 1,10-Phenanthroline Derivatives

As the rapid development of modern industry, people have the higher requirements about the material performance and the relative research is deepening gradually, so more and more researchers focus their view on the exploitation of functional materials which have the specific function such as optical, electrical, magnetics and catalytic properties. In this respect, the complexes which combined the peculiarity of inorganic metal ions and organic ligands, have the diversities, novelty, controllability of unit structure and have great potential for application in adsorption separation, energy storage, optics, electricity, magnetism, catalysis, drug delivery and retarded release, etc., so complexes get the universal attention by researchers all over the world. For a long time, it is the target of many researchers to make the complexes which have objective structure and the corresponding functional properties based on the simple material.Herein, we consider to design novel structure and functionality of complexes, and choose a series of 1,10-phenanthroline derivatives which were used as nitrogen-containing ligands, in combination with organic multi-carboxylate or polyanion system, by the self-assembly reactions with metal ions, synthesized 21 new complexes successfully. We characterized the structures of complexes and researched carefully the photochemical and photophysical properties of complexes. The specific research works was as follows:(1) The development of coordination chemistry, synthesis methods, impact factors and application areas of complexes were introduced. The research progression of complexes based on 1,10-phenanthroline derivatives was summarized, and the research basis of this article was put forward.(2) Six novel complexes, namely [Pb(1,4-bdoa)(TTBT)]n (1), [Zn(1,4-bdoa)(DPPZ)(H2O)]n (2), [Cd(l,4-bdoa)(DPPZ)]n (3), [Fe(1,4-bdoa)(DPPZ)2]o.5n·2nH20 (4), Co(1,4-bdoa)(DPPZ)2]n-2nH20 (5) and [Co2(1,4-bdoa)(1,4-Hbdoa)(DPPZ)2(OH)]n·3nH2O (6) were hydrothermally synthesized with 1,10-phenanthroline derivatives and benzene-1,4-dioxyacetic acid (1,4-H2bdoa) as the mixed ligand and Pb(II), Zn(II), Cd(II), Fe(II), Co(II) ions as metal center (TTBT 10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene, DPPZ= dipyrido[3,2-a:2’,3’-c]phenazine). Then we characterized the structures of complexes through single-crystal X-ray diffraction, infrared (IR) spectrum, power X-ray diffraction (XRD), thermogravimetry analysis (TGA), element analysis and ultraviolet-visible (UV-vis) absorption spectrum. We analyzed detailedly the affecting factors of the structure of complexes and studied the photoluminescence, magnetism, and photocatalytic activities. Complexes 1-3 all exhibited excellent photoluminescent properties at room temperature, and the antiferromagnetic interaction existed in 6. Complex 1 represented good performance for the photocatalytic degradation of organic dyes (methyl violet (MV), methylene blue (MB), and rhodamine B (RhB)) in the aqueous solution under UV irradiation, the photocatalytic mechanism was proposed with 1 and a simple photodegradation model was built up. Complex 2 could be as a photocatalyst for degradation of organic dyes in the presence of H2O2.(3) Six new complexes, namely [Pb(2,4’-bpdc)(DPPZ)]n·nH2O (7), [Cd(2,4’-bpdc)(DPPZ)]n (8), [Zn(2,4’-Hbpdc)2(DPPZ)] (9), [Fe(2,4’-bpdc)(DPPZ)(H2O)]n (10), [Cu(2,4’-bpdc)(DPPZ)(H2O)]n (11) and [Co2(2,4’-bpdc)2(PyPhen)2]n(12) were synthesized with 1,10-phenanthroline derivatives and 2,4’-biphenyldicarboxylic acid (2,4’-H2bpdc) as the mixed ligand and Pb(Ⅱ), Cd(Ⅱ), Zn(Ⅱ), Fe(Ⅱ), Cu(Ⅱ), Co(Ⅱ) ions as metal center (PyPhen= pyrazino[2,3-f][l,10]-phenanthroline). The structures of these complexes were determined by single-crystal X-ray diffraction analysis and further characterized by IR spectrum, power XRD, TGA, element analysis and UV-vis absorption spectrum. Factors of influencing complexes structure was analyzed in detail, the experimental results showed that metal ions and coordination modes of the ligand could significantly affect the structure of the complexes. Complexes 7-9 all exhibited excellent photoluminescence. In addition, complex 9 had good activity of photocatalytic degradation of MB in the presence of H2O2.(4) Four new complexes, viz. [Pb(DDA)0.5(PTCP)(NO3)]·H2O (13), [Co(DDA)(PTCP)2(H2O)]·0.5H2DDA·H2O (14), [Pb(DDA)0.5(TCPP)(NO3)]n (15) and [Pb(DDA)0.5(TCPB)]n (16), based on 1,10-phenanthroline derivatives and H2DDA (PTCP= 2-phenyl-lH-1,3,7,8-tetra-azacyclopenta[1]phenanthrene, TCPP= 2-(1H-1,3,7,8-Tetraaza-cyclopenta[1]phenanthren-2-yl)-phenol, TCPB 2-(1H-1,3,7,8-Tetraaza-cyclopenta[l]phenanthren-2-yl)-benzoic acid, H2DDA 1,12-dodecanedioic acid) as the mixed ligands coordinated with Pb(Ⅱ) and Co(Ⅱ), were synthesized. We used different testing methods to characterize the crystal structure of the complexes, for example, IR spectrum, power XRD, TGA, element analysis and UV-vis absorption spectrum, etc. Factors of influencing complexes structure was analyzed, the structure of the complexes could be changed by altering nitrogen-containing ligand, metal center, types of anions and the ratio of the reactants. Natural bond orbital (NBO) analysis of 13 was performed by the B3LYP/LANL2DZ method in Gaussian 09 Program. Furthermore, complexes 13,15 and 16 exhibited excellent photoluminescence at room temperature.(5) Five complexes, viz. [Cu(DPPZ)(H20)Cl]6[PW,204o]2·6H20 (17), [Cu2(DPPZ)2(H20)3Cl][PW1204o]·H20 (18), [Cu(DPPZ)(H2O)Cl]6[PMo,2O40]2 (19), [Cu4(DPPZ)4(H2O)8Cl2][PMo12O40]2·10H2O (20) and [Zn2(TCPB)4][H4SiW,2040] (21), were synthesized successfully by the reaction of 1,10-phenanthroline derivatives, a-Keggin polyoxometalates (POMs) and Cu(II), Zn(II) metal ions. A variety of detection methods were used to characterize the crystal structures of the complexes. The factors of influencing complexes structure were analyzed in detail, and the photocatalytic activities of the complexes were mainly studied. Structural analyses revealed that inorganic anions (POMs and Cl-, etc.), pH value in reaction system and the nature of the ligand all could influence the structures of the complexes. Five complexes all had outstanding photocatalytic activity for degradating MB in the presence of H2O2.(6) We summarized the researching work of this topic and prospected the further research.