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Molecular lanthanide and actinide compounds with chalcogenolate ligands

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Title
Molecular lanthanide and actinide compounds with chalcogenolate ligands
Name (type = personal)
NamePart (type = family)
Wu
NamePart (type = given)
Wen
NamePart (type = date)
1992-
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Wen Wu
Role
RoleTerm (authority = RULIB)
author
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Brennan
NamePart (type = given)
John G.
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John G. Brennan
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Advisory Committee
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chair
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NamePart (type = family)
Goldman
NamePart (type = given)
Alan
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Alan Goldman
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Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Asefa
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Tewodros
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Tewodros Asefa
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Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
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Riman
NamePart (type = given)
Richard
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Richard Riman
Affiliation
Advisory Committee
Role
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outside member
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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 (encoding = w3cdtf); (qualifier = exact)
2019
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2019-05
CopyrightDate (encoding = w3cdtf); (qualifier = exact)
2019
Language
LanguageTerm (authority = ISO 639-3:2007); (type = text)
English
Abstract
A series of novel molecular lanthanide and actinide chalcogenolate compounds have been prepared with different neutral donor ligands. Three lanthanide fluorinated selenolate monomers (DME)2Ln(SeC6F5)3 (Ln = Nd, Er, Tm, DME = 1,2-Dimethoxyethane) were synthesized in high yields by reductive cleavage of the Se-Se bond in (SeC6F5)2 with elemental Ln in DME. Their structural and optical properties are discussed. Emission measurements indicate that these compounds are bright NIR sources. A number of dimeric thorium disulfide and diselenide compounds have been prepared with sterically undemanding ancillary chalcogenolate ligands. Five complexes, (py)6Th2I4(S2)2 (py)6Th2Br2(SC6F5)2(S2)2, (py)6Th2I4(Se2)2, (py)6Th2I2(SC6F5)2(Se2)2, and (py)6Th2Br2(SC6F5)2(Se2)2 (py = pyridine) were isolated in high yields by first reducing mixtures of metal Th, chalcogenolate ligands and halide sources (I2 or PhSeBr) in py, followed by in-situ ligand based redox reactions with elemental sulfur or selenium. These are the first examples of thorium compounds with bridging dichalcogenide ligands. Attempts to prepare chloride derivatives gave mixtures of (py)4ThCl4 and either (py)6Th2Cl2(SC6F5)2(S2)2 or (py)8Th4Se4(SePh)4(SC6F5)4. A computational analysis of experimental 77Se NMR chemical shifts reveals that the dimeric structures with two bridging dichalcogenides are maintained in solution. Thermolysis of (py)6Th2I4(Se2)2 leads to the formation of solid-state ThSe2 and I2. The identities of chalcogenolate ligands and neutral donor ligands have been found to influence the structures of thorium compounds. Three Th monomers, (bipy)2Th(SC6F5)4, (Hpz)4(pz)Th(SC6F5)3 (Hdmpz)2(dmpz)2Th(SC6F5)2 and three Th dimers, (pzn)4Th2(SC6F5)8, (Hpz)4(pz)2Th2(SePh)6 (Hdmpz)4(dmpz)2Th2(SC6F5)6 (bipy=2,2’-bipyridine, pzn = pyrazine; Hpz = pyrazole, Hdmpz= 3,5 dimethylpyrazole) have been prepared and characterized. Reaction of Th, (SeC6F5)2 and Hpz in toluene also results in a thorium cluster (Hpz)8Th4Se4(SeC6F5)8 with Th4Se4 cubane core. Several thorium and uranium oxo- and fluoro- compounds were also synthesized. Oxo compounds (py)6Th2O(Se2)I4, (py)6U2O(Se2)I4, and (py)10Th6O3(Se2)8(SC6F5)2 were prepared by adding elemental Se and SeO2 into the mixture of metal Th or U, chalcogenolate ligands and halide sources in py. Two fluoride complexes have also been prepared. Coming from the reactions of metal Th or U, (SC6F5)2 and I2 in py, (py)4ThI3F contains fluoride from the original (SC6F5)2; while the uranium derivative, (py)3UI3(SC6F5) follows stoichiometry of the starting materials.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
RelatedItem (type = host)
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Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_9776
PhysicalDescription
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application/pdf
InternetMediaType
text/xml
Extent
1 online resource (xiv, 161 pages) : illustrations
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Subject (authority = ETD-LCSH)
Topic
Ligands (Biochemistry)
Subject (authority = ETD-LCSH)
Topic
Inorganic compounds
RelatedItem (type = host)
TitleInfo
Title
School of Graduate Studies Electronic Theses and Dissertations
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rucore10001600001
Location
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NjNbRU
Identifier (type = doi)
doi:10.7282/t3-0pj8-nt97
Genre (authority = ExL-Esploro)
ETD doctoral
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The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Wu
GivenName
Wen
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2019-04-11 01:28:35
AssociatedEntity
Name
Wen Wu
Role
Copyright holder
Affiliation
Rutgers University. School of Graduate Studies
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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.
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Type
Embargo
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2019-05-31
DateTime (encoding = w3cdtf); (qualifier = exact); (point = end)
2019-11-30
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after November 30th, 2019.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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2019-04-11T01:11:08
DateCreated (point = end); (encoding = w3cdtf); (qualifier = exact)
2019-04-11T01:11:08
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