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Synthesis of pincer-ligated metal complexes for dehydrogenation, nitrogen reduction, and OLED applications

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Title
Synthesis of pincer-ligated metal complexes for dehydrogenation, nitrogen reduction, and OLED applications
Name (type = personal)
NamePart (type = family)
Casuras
NamePart (type = given)
Andrea Frances Koslow
NamePart (type = date)
1991-
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Andrea Frances Koslow Casuras
Role
RoleTerm (authority = RULIB)
author
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Goldman
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Alan S
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Alan S Goldman
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Advisory Committee
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chair
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O'Carroll
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Deirdre
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Deirdre O'Carroll
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Advisory Committee
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internal member
Name (type = personal)
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Warmuth
NamePart (type = given)
Ralf
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Ralf Warmuth
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Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Jaekle
NamePart (type = given)
Frieder
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Frieder Jaekle
Affiliation
Advisory Committee
Role
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outside member
Name (type = corporate)
NamePart
Rutgers University
Role
RoleTerm (authority = RULIB)
degree grantor
Name (type = corporate)
NamePart
School of Graduate Studies
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (qualifier = exact)
2019
DateOther (qualifier = exact); (type = degree)
2019-01
CopyrightDate (encoding = w3cdtf)
2019
Place
PlaceTerm (type = code)
xx
Language
LanguageTerm (authority = ISO639-2b); (type = code)
eng
Abstract (type = abstract)
After the initial development of pincer complexes in the 1960’s, a significant amount of research has been placed into the understanding and applications of pincer complexes. To this day, new applications of pincer-ligated complexes are being discovered. While most commonly used in catalysis, recently pincer-ligated complexes have expanded to other fields, such organic light-emitting devices (OLEDs). This thesis will focus on the synthesis of several pincer-ligated complexes and their application towards dehydrogenation, nitrogen reduction, and OLEDs.
Synthesis of the reported Nishibayashi molybdenum-dimer, the (tBuPNP)MoNCl, and the (tBuPPP)MoNCl complexes were attempted for use in electrochemical nitrogen reduction. Due to the ability of the Nishibayashi complexes to reduce dinitrogen to ammonia chemically, we synthesized them in attempt to do the reduction electrochemically instead. In addition, synthesis of (tBuPPP)RuNCl and (tBuPPP)ReNCl complexes were attempted for comparison to the molybdenum analogue. Lastly, we attempted to synthesize a pyrene-PNP ligand for potential ligand-electrode interactions. After the attempt reported here, the pyrene-PNP ligand was successful synthesized by a different route in our laboratory.
After DFT calculations and experiments showed that ruthenium was not a good choice for nitrogen reduction, the (tBuPPP)Ru complex was then considered for dehydrogenation work. Several new (tBuPPP)Ru complexes were synthesized and characterized via NMR. Preliminary studies have shown that the (tBuPPP)RuH4 complex is an effective catalyst for alcohol dehydrogenation and has good potential for alkane dehydrogenation as well.
Another aspect of dehydrogenation work is the acceptor that is used during catalysis. With the goal of doing dehydrogenation electrochemically, benzoquinone was chosen as a potential acceptor. The interactions of benzoquinone, and several benzoquinone derivatives, with (tBuPCP)IrH2/H4 were studied. It was observed that quinones are extremely efficient hydrogen acceptors; however, the excess quinone can then strongly bind to iridium, inhibiting any alkane dehydrogenation. We were able to achieve a slow production of ketone from alcohol dehydrogenation, showing that, while strong, the quinone-metal bond can be broken, allowing catalysis.
While (tBuPCP)Ir complexes are extremely well known in the literature for catalysis, their photoluminescence is not usually considered. Several different (tBuPCP)Ir complexes with polycyclic aromatic ligands were studied for their photoluminescence. By making small variations on the polycyclic ligand, we were able to observe the effects these variations had on the emission wavelength. Additionally, each complex was mixed with polymethylmethacrylate (PMMA) and spin coated on a glass surface to examine their performance and lifetime in the solid state, as they would be in an OLED.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (authority = local)
Topic
Organic light-emitting devices
Subject (authority = local)
Topic
Pincer-ligated complexes
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_9424
PhysicalDescription
Form (authority = gmd)
electronic resource
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application/pdf
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text/xml
Extent
1 online resource (181 pages : illustrations)
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Andrea Frances Koslow Casuras
RelatedItem (type = host)
TitleInfo
Title
School of Graduate Studies Electronic Theses and Dissertations
Identifier (type = local)
rucore10001600001
Location
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NjNbRU
Identifier (type = doi)
doi:10.7282/t3-w1wa-r746
Genre (authority = ExL-Esploro)
ETD doctoral
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The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Casuras
GivenName
Andrea
MiddleName
Frances Koslow
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2018-12-12 21:22:28
AssociatedEntity
Name
Andrea Casuras
Role
Copyright holder
Affiliation
Rutgers University. School of Graduate Studies
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
Copyright
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Copyright protected
Availability
Status
Open
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Permission or license
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2018-12-22T16:15:26
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