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Molecular lanthanide fluorides

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TypeOfResource
Text
TitleInfo
Title
Molecular lanthanide fluorides
SubTitle
photoluminescence from novel architectures
Identifier
ETD_2356
Identifier (type = hdl)
http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000052146
Identifier (type = doi)
doi:10.7282/T3PG1RW8
Language
LanguageTerm (authority = ISO 639-3:2007); (type = text)
English
Genre (authority = marcgt)
theses
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (authority = ETD-LCSH)
Topic
Lanthanum compounds
Subject (authority = ETD-LCSH)
Topic
Organofluorine compounds
Subject (authority = ETD-LCSH)
Topic
Photoluminescence
Abstract (type = abstract)
Novel molecular lanthanide (Ln) species have been prepared that showcase not only their exceptional optical properties but also deviations from the "typical" reaction/product schemes realized over the past few decades. Ln chalcogenolates [(L)xLn(SC6F5)3 and (L)xLn(SeC6F5)3; (Ln = Pr, Nd, Sm, Er, or Yb; L = pyr, DME, or THF); x = 3 or 4] have been prepared and their optical and structural properties are discussed. The photoluminescence quantum efficiency (QE), radiative decay, and effective bandwidth for the 4F11/2 --> 4I9/2 transition of Nd(SC6F5)3(DME)3 were found to be 9%, 1.39ms, and 59nm, respectively. At the time, this was one of the highest reported quantum efficiencies for a molecular Nd species.
Ligand, metal radii, and neutral donor molecule have been found to influence the physical and optical properties of these species. By changing any one of these variables, vastly different products can arise; for example, 7-coordinate [Nd(SC6F5)3(THF)3]2 with bridging thiolates , 7-coordinate Nd(SeC6F5)3(THF)3 , and 8-coordinate Nd(SC6F5)3(DME)2, have all been successfully isolated. Using the same ligand and neutral donor with Er gives 6-coordinate Er(SeC6F5)3(THF)3, a near perfect octahedral geometry with a significant structural trans influence. DFT calculations indicate that the trans influence in these bond lengths result from covalent Ln-E interactions.
Cluster compounds DME3Yb4F2O(OCH2CH2OCH3)2(SeSe)(SC6F5)4•DME and
(pyr)24Ln28F68(SePh)16 (Ln = Ce, Nd, Pr) have been prepared by C-F bond activation and direct fluoride source (NH4F), respectively. At 41%, the 4F11/2 --> 4I9/2 transition of (pyr)24Nd28F68(SePh)16 has the highest QE to date for any molecular Nd species.
(pyr)xM(SeC6F5)2 (M = Zn, Cd, Hg and x = 0 or 2) were synthesized by reductive cleavage of F5C6SeSeC6F5 by the respective metals. Both the Zn and Cd species have tetrahedral coordination environments. The Hg analog has a near linear, modulated structure, with no coordinated pyridine ligands. These molecular II-VI semiconductor precursors melt between 115 and 175°C and when heated to 650°C under reduced pressures, give crystalline MSe (M = Zn, Cd, Hg) products.
PhysicalDescription
Form (authority = gmd)
electronic resource
Extent
xvi, 166 p. : ill.
InternetMediaType
application/pdf
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text/xml
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Michael Dennis Romanelli
Name (type = personal)
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Romanelli
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Michael Dennis
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author
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Michael Dennis Romanelli
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Garfunkel
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Eric
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chair
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Eric L Garfunkel
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Brennan
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John
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internal member
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John G Brennan
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Potenza
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Joseph
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internal member
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Joseph A Potenza
Name (type = personal)
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Goldman
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Alan
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Alan Goldman
Name (type = personal)
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Riman
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Richard
Role
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outside member
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Richard E Riman
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
OriginInfo
DateCreated (encoding = w3cdtf); (qualifier = exact)
2010
DateOther (encoding = w3cdtf); (qualifier = exact); (type = degree)
2010-01
Place
PlaceTerm (type = code)
xx
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
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NjNbRU
Genre (authority = ExL-Esploro)
ETD doctoral
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Rights

RightsDeclaration (AUTHORITY = GS); (ID = rulibRdec0006)
The author owns the copyright to this work.
Copyright
Status
Copyright protected
Notice
Note
Availability
Status
Open
Reason
Permission or license
Note
RightsHolder (ID = PRH-1); (type = personal)
Name
FamilyName
Romanelli
GivenName
Michael
Role
Copyright Holder
RightsEvent (ID = RE-1); (AUTHORITY = rulib)
Type
Permission or license
Label
Place
DateTime
2009-12-29 12:23:12
Detail
AssociatedEntity (ID = AE-1); (AUTHORITY = rulib)
Role
Copyright holder
Name
Michael Romanelli
Affiliation
Rutgers University. Graduate School - New Brunswick
AssociatedObject (ID = AO-1); (AUTHORITY = rulib)
Type
License
Name
Author Agreement License
Detail
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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Technical

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application/x-tar
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