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Novel lanthanide structures

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TitleInfo
Title
Novel lanthanide structures
SubTitle
fluorinated alkoxides, chalcogenido alkoxides, fluorides, and oxychalcogenido clusters
Name (type = personal)
NamePart (type = family)
Norton
NamePart (type = given)
Kieran James
NamePart (type = date)
1981-
DisplayForm
Kieran Norton
Role
RoleTerm (authority = RULIB)
author
Name (type = personal)
NamePart (type = family)
Brennan
NamePart (type = given)
John G
DisplayForm
John G Brennan
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
chair
Name (type = personal)
NamePart (type = family)
Goldman
NamePart (type = given)
Alan S
DisplayForm
Alan S Goldman
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Li
NamePart (type = given)
Jing
DisplayForm
Jing Li
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Riman
NamePart (type = given)
Richard E
DisplayForm
Richard E Riman
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
outside member
Name (type = corporate)
NamePart
Rutgers University
Role
RoleTerm (authority = RULIB)
degree grantor
Name (type = corporate)
NamePart
Graduate School - New Brunswick
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (qualifier = exact)
2014
DateOther (qualifier = exact); (type = degree)
2014-01
Place
PlaceTerm (type = code)
xx
Language
LanguageTerm (authority = ISO639-2b); (type = code)
eng
Abstract (type = abstract)
A number of novel lanthanide alkoxide species were synthesized with fluorinated ligands. This includes monomers with pentafluorophenol, (DME)2Ln(OC6F5)3 (Ln = Nd, Er, Tm, Eu, and Yb), (py)4Ln(OC6F5)3 (Ln = Eu, Tb, Er, Tm, Yb), and (THF)3Yb(OC6F5)3. Unique europium species, ((py)3Eu(CF3SO3)2)n, (DME)2Eu(µ-OC6F5)3Eu(µ-OC6F5)3Eu(DME)2, and (DME)( C6F5O)2Eu(µ-OC6F5)3Eu(DME)2, were also produced. Most reactions proceeded by metathesis of lanthanide chalcogenolates, but direct redox reaction of elemental lanthanide with C6F5OH or CF3SO3H catalyzed by Hg also proved to be viable routes. The Eu(II) trimer was only synthesized through direct oxidation of the metal with the alcohol. Photoluminescence of (DME)2Ln(OC6F5)3 (Ln = Nd, Er, Tm) was tested, and they exhibited high quantum efficiency for lanthanide monomers. Two series of dimers, (py)6Ln2(OC6F5)2(µ-η2-SS)2 (Ln = Sm, Eu, and Gd) and (py)6Ln2(CF3SO3)2(Se)x (Ln = Sm, Tm, Yb, and Lu; x = 3 or 4), were synthesized via substitution of EPh-. The europium dimer is the first example of a Eu(III) molecular sulfido species which is extremely dark due to strong, broad LMCT from the sulfido. The selenidos display a conspicuous coordination change resulting from the relatively small difference in Ln ionic radii forming (py)6Ln2(CF3SO3)2(µ-η2-SeSe)( µ-Se) for small late lanthanides and (py)6Ln2(CF3SO3)2(µ-η2-Se)2 for larger early lanthanides. Three fluorido clusters were synthesized without the use of traditional fluoride sources. (DME)6(py)6Nd18(C6F5O)18 F24O3S3 was produced from a reaction of neodymium phenylselenolate with C6F5OH and sulfur. (py)8Yb4F8(CF3SO3)4 and (DME)4Tb4(CF3SO3)6F2S2 were synthesized from lanthanide chalcogenolates, elemental chalcogens, and CF3SO3H. Cleavage of C-F bonds to form these clusters appears to be a slow reaction. Most reactions producing them took several months. Lanthanide oxychalcogenido clusters were produced from reacting lanthanide chalcogenolates with pySO3 or TeO2 and Te. (THF)8Ln8O2S2(SePh)16 (Ln = Ce, Nd) clusters were synthesized from “Ln(SePh)3” and pySO3. Reactions of “Ln(TePh)3”, TeO2 and Te produced [(py)5Ln3O(Te2)3(TePh)][(py)7Ln4Te(Te2)2(Te2Te(Ph)Te2)(TePh)] (Ln = Ho, Er), [(etpy)11Ho6O4Te4TePh] [Hg(TePh)3] and [(4etpy)12Yb6O4Te4][Hg(TePh)3] [(TePh)3].
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_5281
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
xi, 166 p. : ill.
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Kieran James Norton
Subject (authority = ETD-LCSH)
Topic
Rare earth metals
Subject (authority = ETD-LCSH)
Topic
Chalcogens
Subject (authority = ETD-LCSH)
Topic
Rare earth fluorides
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier (type = doi)
doi:10.7282/T3H9939J
Genre (authority = ExL-Esploro)
ETD doctoral
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RightsDeclaration (ID = rulibRdec0006)
The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Norton
GivenName
Kieran
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2014-01-03 11:29:45
AssociatedEntity
Name
Kieran Norton
Role
Copyright holder
Affiliation
Rutgers University. Graduate School - New Brunswick
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Name
Author Agreement License
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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
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Open
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Permission or license
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