Study On Crystal Structures Of Alkoxy Substituted Phthalocyanines And Optical Recording Material

The phthalocyanines have some special characteristics such as, with large stable conjugated system, their special optical properties and chemical activities, which led to their use as dye and pigment, and potentials in the high tech applications as functional materials, molecular-scale devices, and the use as medicine because of their structure alike to the porphyrin. In the different applications, to obtain the required physical and chemical properties, the structure of phthalocyanine molecule has to be modified. The highly modifiable of phthlocyanine molecule makes convenience to the modification of the molecule to fit the special applications, also pose problems to the investigation of structure-properties relationship at the same time. The main results in this dissertation are summarized as follows:1. Phthalocyanines substituted with alkoxy of different types and with different number (4 or 8) were synthesized. The complex suitable for the recording layer of CD-R (CD-R dye) was selected and appraised. Among these complexes, the center atoms are Cu, Ni, Zn, Co, VO, and H2 (metal free), the alkoxy groups include ethoxy, butoxy, iso-pentoxy, and 2,2,4-trimethyl-3-pentoxy, respectively. Methods used in the syntheses are the condensations of phthalonitrile derivatives at the presence of strong organic base (DBU) or lithium in alcohol solvent, at the presence of ammonium molybdate in the inert solvent, and the coordination reactions of the metal salt with metal free phthalocyanine.2. Thirteen single crystals of these complexes were obtained and the structures of them were determined:(1) (CH3CH2O)8PcCu, (2) [CH3(CH2)3O]8PcH2, (3) [CH3(CH2)3O]8PcCu, (4) [CH3(CH2)3O]8PcNi, (5) [CH3(CH2)3O]8PcCo, (6) [CH3(CH2)3O]8PcCo(CH3OH)(Py). (7) [(CH3)2(CH2)3O]8PcCu, (8) [(CH3)2(CH2)3O]8PcNi, (9) [(CH3)2(CH2)3O]8PcCo, (10) [CH3(CH2)7O]8PcVO,The main features of these structures are:(1) The central part of the molecules of the tetra-substituted complexes with no substituents neighbored maintains planar conformation. The introduce of substituents makes remarkable changes of molecular packing where the spaces between neighboring ring systems are distanced to ~7A, larger than ~3.5A in the stacking of non-substituted phthalocyanine molecules, and the bigger holes formed between molecules take it easy to entrances for solvent molecules.(2) One characteristic of octa-substituted complexes is the saddle conformation of the molecules. That is, the steric effect of the neighboring substituents causes the deviation of the ring system, so the bigger substituent led to the larger deviation. This result is consistent to that of M. J. Cook. Based on the comparison of a series of compounds with different substituents, a newly revealed relationship in our works is obtained which indicate that the deviation of ring system from planar conformation is the co-effect of steric block of neighboring substituents of inner molecule and the influence of the aggregation between the molecules.3. Based on the results of crystal structures, combined with the spectra and thermal measurements, the relationship between the structures and properties were studied, mainly for what are important to the CD-R, for example, the UV/vis spectra, solubility, and thermal stability, et al. The understandings of these aimed at the development of the CD-R dye.