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6-8-2017 Sturtz Thesis Final.pdf (18.77 MB)

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Synthesis and Structural Chemistry of Diamagnetic Dimeric Metal Phthalocyanines

Sturtz, Benjamin Walden
http://rave.ohiolink.edu/etdc/view?acc_num=case1496922051865658

Abstract Details

2017, Doctor of Philosophy, Case Western Reserve University, Chemistry.
Synthesis and Structural Chemistry of Diamagnetic Dimeric Metal Phthalocyanines Abstract by BENJAMIN 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.
Malcolm Kenney, Dr. (Advisor)
Michael Zagorski, Dr. (Committee Chair)
John Protasiewicz, Dr. (Committee Member)
Anna Samia, Dr. (Committee Member)
Wiley Youngs, Dr. (Committee Member)
350 p.
Chemistry
phthalocyanine; naphthalocyanine; octamethylporphyrin; octaethylporphyrin; aluminum; silicon; gallium; germanium; tin; scandium; dimer; crystal structure; ring-to-ring bonding; pigment; dye

Recommended Citations

Citations

  • Sturtz, B. W. (2017). Synthesis and Structural Chemistry of Diamagnetic Dimeric Metal Phthalocyanines [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1496922051865658

    APA Style (7th edition)

  • Sturtz, Benjamin. Synthesis and Structural Chemistry of Diamagnetic Dimeric Metal Phthalocyanines. 2017. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1496922051865658.

    MLA Style (8th edition)

  • Sturtz, Benjamin. "Synthesis and Structural Chemistry of Diamagnetic Dimeric Metal Phthalocyanines." Doctoral dissertation, Case Western Reserve University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=case1496922051865658

    Chicago Manual of Style (17th edition)

case1496922051865658
420
© 2017, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.