Structural Chemistry of Silicon Phthalocyanines

Structures of a number of silicon phthalocyanines have been investigated using both experimental and theoretical methods. Single crystal structures have been determined for some of these silicon phthalocyanines. Various theoretical methods, including the density functional theory (DFT), atoms-in-molecules (AIM), reduced-density-gradient (RDG), and Monte-Carlo methods have been utilized to understand these structures.The first part of the thesis is focused on the structures of ¿¿-oxygen bridged silicon phthalocyanine oligomers. We report the crystal structures of two matching sets of such compounds for the first time. The staggering angles in these phthalocyanines lead to the conclusion that interactions exist between adjacent rings. AIM and RDG methods have revealed some important properties of these interactions. They are long-range, directional and significant, and can be distinguished from both covalent bonds and van der Waals interactions.The second part of the thesis deals with a sterically crowded silicon phthalocyanine. Its single crystal structure has been determined and it has been found that the phthalocyanine core is highly sterically protected by its ligands and substituents. Semi-empirical and Monte-Carlo calculations of some of its analogues have suggested that the potential for further protection of the phthalocyanine ring is limited.The third part of the thesis describes independent research that has been carried out. This part covers a broad range of chemical topics including bonding, aromaticity, coordination, redox, stability, excitation, electron distribution, Lewis structures, triplet states, and so forth. Both experimentally known and unknown systems are targets in this part. Studies of the hexacoordination and macrocycle effects in the silicon phthalocyanines have revealed distinguishable bond features. Subphthalocyanines incorporating various central atoms have been explored theoretically. Effects caused by axial binding to planar metal macrocycles have been investigated. Some conjugated metal macrocycles whose macrocycles fail to delocalize their unpaired electrons have been studied. The metal-macrocycle coordination in phthalocyanines and subphthalocyanines has been compared. The mechanism by which some metal macrocycles stabilize their triplet states has been investigated.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

Case Western Reserve University School of Graduate Studies

Year dc:date

2013

Author dc:creator

• Yang, Yang

Contributors dc:contributor

• Kenney, Malcolm
• Anderson, Alfred

• Chemistry

Statement dc:rights

• unrestricted
• This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.

Language dc:language

English

Repository record dc:identifier

http://rave.ohiolink.edu/etdc/view?acc_num=case1345752687

OAI identifier oai:identifier

oai:etd.ohiolink.edu:case1345752687