Structural Chemistry Of Macrocyclic Planar Metal Organic Complexes And Nonlinear Optical Properties

Nonlinear optical (NLO) materials have always been an active part in the field of materials research during the last several decades. Now they have extensive applications in the high-speed developing information industry. They not only play an important part in solid state laser technique as frequency-conversion materials, but also have promising applications in the technology of information transmission, storage, extraction, processing and display, etc. At present most attention has been focused on SHG/THG nonlinear material and fluorescence material. It has been confirmed that those compounds with lagre Π conjugation system have large x⁽³⁾ values. Metal-organic coordination complexes can meet this requirement because of their low-energy charge transfer.We have prepared some heterocyclic compounds with N,S-donor as ligands to synthesized ten metal-organic coordination complexes by means of solvent method. X-ray analysis reveals that all the complexes are effectively planar, which could be used as potential third order nonlinear materials. These compounds have been investigated by means of IR, UV and X-ray single crystal analysis. And we give a quantum chemistry calculation to some of them. All the compounds are listed as follows: [Cu₃L₂(H₂O)₂]²⁺·2ClO₄·3H₂O (1); [Ni₂(sthz)₂(H₂O)₄] (2); [CuCl(sthz)]·H₂O (3); three 15 core metallacrown ether with thulium Gd (4); Sm (5) and Pr (6); coordination polymer [CuCl(tha)H₂O]_n (7). Among these compound, (1) exhibits good third order NLO property and dual-photon absorption. (2) and (3) have the same ligand sthz, crystal packing of (3) is a structure of two-dimensional layer supramolecular network ascribed to intramolecular hydrogen bonding interaction, And we compared the IR diagram of ligand with the complex. (4)～(6) are three novel 15-metallacrown-5 prepared with ligand H₂pha, It's the first time we observed such structure. (7) has a one-dimensional comb-like chain to form a coordination polymer. And we also have three other compounds that should get further inverstigation.