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Title Synthesis and Structural Chemistry of Diamagnetic Dimeric Metal Phthalocyanines
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Publication Date
Degree PhD
Discipline/Department Chemistry
Degree Level doctoral
University/Publisher Case Western Reserve University
Abstract Synthesis and Structural Chemistry of Diamagnetic Dimeric Metal PhthalocyaninesAbstractbyBENJAMIN WALDEN STURTZ Syntheses have been developed for 18 new, cofacial, oxygen-bridged, metal phthalocyanine dimers: Me3SiO[SiPcO]2SiMe3, Et3SiO[SiPcO]2SiEt3, Pr3SiO[SiPcO]2SiPr3, PrMe2SiO[SiPcO]2SiMe2Pr, BuMe2SiO[SiPcO]2SiMe2Bu, (i-Bu)3SiO[SiPcO]2Si(i-Bu)3, ThMe2SiO[SiPcO]2SiMe2Th, OdMe2SiO[SiPcO]2SiMe2Od, Ph3SiO[SiPcO]2SiPh3, Ph3SiO[Si0.75Ge0.25PcOSiPcO]SiPh3, Hx3SiO[SiPcOGePcO]SiHx3, Hx3SiO[SiPcOGePcO]SiPh3, Et3SiO[GePcO]2SiEt3, BuMe2SiO[GePcO]2SiMe2Bu, (i-Bu)3SiO[GePcO]2Si(i-Bu)3, Hx3SiO[GePcO]2SiHx3, Ph3SiO[GePcO]2SiPh3, and [GaPc]2O. The structures of these dimers have been determined by single-crystal X-ray crystallography. From the structure data gathered, the distances between the metal centers, the distances between the phthalocyanine ring centroids, and the torsion angles between the phthalocyanines rings have been extracted. The results lead to the conclusion that for centroid-centroid distances of approximately 3.30 Å to 3.40 Å the torsion angles are governed by long distance bonding interactions, LDIs. For distances of approximately 3.40 Å to 3.60 Å the angles are governed by the results of a competition between long distance bonding interactions and crystal packing forces, and for distances above approximately 3.60 Å the angles are governed by crystal packing forces. The known centroid-centroid distance and torsion angle of the cofacial polymer [GaPcF]n further support the governance of the torsion angles in cofacial phthalocyanine systems by a balance of LDI bonding and crystal packing forces. Exploratory structural work on HO[Si(OEP)O]2H and Od(i-Bu)2SiO[SiNcO]2Si(i-Bu)2Od has given data consistent with the existence of preferred torsion angles in these smaller and larger cofacial aromatic systems.
Subjects/Keywords Chemistry; phthalocyanine; naphthalocyanine; octamethylporphyrin; octaethylporphyrin; aluminum; silicon; gallium; germanium; tin; scandium; dimer; crystal structure; ring-to-ring bonding; pigment; dye
Contributors Kenney, Malcolm (Advisor); Zagorski, Michael (Committee Chair)
Language en
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.
Country of Publication us
Format application/pdf
Record ID oai:etd.ohiolink.edu:case1496922051865658
Repository ohiolink
Date Retrieved
Date Indexed 2017-09-11
Grantor Case Western Reserve University

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