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Browne Thesis v.2.2.pdf (16.17 MB)
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Abstract Header
Studies in Organometallic Complexes of Gold and Metallaazadipyrromethenes
Author Info
Browne, Amberle Rose
Permalink:
http://rave.ohiolink.edu/etdc/view?acc_num=case1467835573
Abstract Details
Year and Degree
2016, Doctor of Philosophy, Case Western Reserve University, Chemistry.
Abstract
The formation of metal-carbon bonds is central to organometallic chemistry, but traditional procedures typically suffer from hazards or synthetic difficulties. The Gray laboratory has developed protocols for the transmetalation of aryl groups to metal centers from boron by mild methods. By forming s-bonds between metals such as gold to carbons in luminescent organic scaffolds, interesting changes to the photophysics can result, such as long-lived phosphorescence. These organometallics can be used to access other interesting species and have potential for use in light emitting devices and catalysis. Geminally diaurated arenes featuring gold(I)-gold(I) aurophilic interactions supported by semirigid phosphines were obtained from ligand redistribution reactions of digold dichlorides and digold diaryls in the presence of silver salts with weakly coordinating anions. The isolated complexes were characterized by multinuclear NMR spectroscopy, absorption and emission spectroscopies, combustion analysis, and 77 K emission lifetimes, as well as X-ray diffraction crystallography, when possible. Three complexes were crystallographically authenticated. Aromaticity of the geminally diaurated arenes was slightly disrupted. Metallaboroxines, unlike organic boroxines, are a seldom reported class of compounds and rational synthetic methodologies are lacking. Boroxinato gold(III) compounds were obtained in arrested transmetalation reactions of boronic acids and cyclometalated gold(III) trifluoroacetates. The boroxinato gold(III) complexes are the first metallaboroxines characterized by photophysical means, and they displayed phosphorescence with microsecond long lifetimes. Four complexes were crystallographically authenticated. All complexes were characterized by multinuclear NMR spectroscopy, absorption and emission spectroscopies, combustion analysis, 298 K and 77 K emission lifetimes, X-ray crystallography, and relative quantum yields. A silicon analogue was isolated by a similar procedure that was characterized by NMR, absorption and emission spectroscopies, combustion analysis, X-ray crystallography, and relative quantum yields. Brominated azadipyrromethenes were successfully ligated to cyclometalated iridium(III) centers by transmetalation from the BF2- chelates of azadipyrromethenes. Luminescence was not detected from these compounds. The protocol was extended to include an unbrominated azadipyrromethene to investigate if the compound would display luminescence if the heavy element, bromine, was uninvolved. The complex was characterized by NMR, absorption and emission spectroscopies, and combustion analysis.
Committee
Genevieve Sauve (Committee Chair)
John Protasiewicz (Committee Member)
Malcolm Kenney (Committee Member)
Horst von Recum (Committee Member)
Thomas Gray (Advisor)
Pages
367 p.
Subject Headings
Chemistry
Keywords
gold
;
organometallics
;
azadipyrromethene
;
boroxine
;
transmetalation
;
geminal diauration
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Citations
Browne, A. R. (2016).
Studies in Organometallic Complexes of Gold and Metallaazadipyrromethenes
[Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1467835573
APA Style (7th edition)
Browne, Amberle.
Studies in Organometallic Complexes of Gold and Metallaazadipyrromethenes.
2016. Case Western Reserve University, Doctoral dissertation.
OhioLINK Electronic Theses and Dissertations Center
, http://rave.ohiolink.edu/etdc/view?acc_num=case1467835573.
MLA Style (8th edition)
Browne, Amberle. "Studies in Organometallic Complexes of Gold and Metallaazadipyrromethenes." Doctoral dissertation, Case Western Reserve University, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=case1467835573
Chicago Manual of Style (17th edition)
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Document number:
case1467835573
Download Count:
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Copyright Info
© 2016, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.