| Nonlinear Optical Materials (NOMs) are the potential discovery of novel functional materials expected to find application in the broad areas of frequency-changing, laser modulation and deflexion, and Q switch and so on. So researches on NOMs are so important and still active for the light-signal processing, transferring and operation. Based on the highlight of molecular design for the NOMs and the flexibility in structures of organic molecule, the author picks the pyridine with an electron donating-withdrawing functional group as a mother reagent to prepare or synthesize some NOM crystal materials by use of solution crystal growing technique, hydrothermal synthesis route and so on, in fitting of the structural requirements for NOMs along a line of the relationship between molecular structure and material functions. In this thesis, about 10 NOM crystals, namely POA II (1), [Zn(POA)2(H2O)2] (2), [Zn(POA)2(H2O)2]·2H2O (3), [Mn(POA)2(H2O)2]·2H2O (4), [Cu(POA)2]n (5), [Cu(POA)2]n (6), [Cu(pica)2ClO4]n (7), [Cu(pica)2]n·2nH2O (8), [Pd2(phz)2Cl2](9) and [Mn(ashz)·H2O]6 (10), (where POA = 4-nitroxyl-2-picolinic acid-1-oxygen, pica = 2-pyridine carboxylate, phz = 2-picoloylhydrazide and ashz = N-acyl-N'-(5-nitrosalicylhydrazide)), of which 6 crystals (1～6) belonged to the pyridyl-oxo-derivant system, 3 crystals (7～9) attributed to pyridyl-acyl-derivant system and the rest crystals (10) come from pseudooxo-pyridyl-derivant system, have been tailor-synthesized. The structures of such 10 crystals have been determined by single crystal X-ray diffraction, and their element chemical analysis, FT-IR and UV-VIS spectra, DSC and TGA traces, doubling frequency optical effect, fluorescence and electronic density calculation have also been carried out. The results show that those 10 compounds crystallized in several different structural types. Compound 1, crystallized in orthorhombic chiral P212121 space group, has the molecular weaker H-bond interaction, and compounds 2～6 are a series of coordination complexes with the distorted octahedronal coordination metal centers based on 1 as ligand building blocks having aromatic π-π interactions in the 3～4, of which 2 and 3 are inner isomers that 2 has two of dissymmetrical equator POA ligands but 3 is symmetrical complex, 3 and 4 are allomers while 5 and 6 are 1D coordination polymeric isomers with bridging POA ligands. Compounds 7～8 are 1 D coordination polymers with a novel bridging ClO4 ligand and a bridging pica ligand, respectively, while 9 is a 0D discrete butterfly type complex with binuclear {Pd2}... |
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