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Structural diversity in metal-organic materials

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Material Information

Title:
Structural diversity in metal-organic materials
Physical Description:
Book
Language:
English
Creator:
McManus, Gregory J
Publisher:
University of South Florida
Place of Publication:
Tampa, Fla
Publication Date:

Subjects

Subjects / Keywords:
Crystal structure
Coordination polymer
Crystal engineering
Supramolecular isomerism
Topology
Dissertations, Academic -- Chemistry -- Doctoral -- USF   ( lcsh )
Genre:
non-fiction   ( marcgt )

Notes

Abstract:
ABSTRACT: The interest in metal-organic materials namely, coordination polymers and metal-organic frameworks has risen dramatically over the past few years. To a certain extent this interest is a consequence of the realization chemists have discovered how to play a form of molecular Lego® in which metal cations or metal clusters represent the bricks (or nodes) and organic ligands such as 4,4-bipyridine (bipy) or benzene-dicarboxylate represents the glue (or spacers). The "node-and-spacer" approach to self-assembly can be invoked in such a manner that a plethora of infinite architectures and discrete polyhedra can be generated from geometric principles, some of which are unprecedented in either natural or synthetic materials. The research presented within this dissertation primarily involves the use of coordination chemistry and supramolecular chemistry in the context of synthesizing metal-organic materials and deals with how subtle variations in reactants and procedures can have dramatic effects upon the materials formed. The effect of aromatic guest molecules on the crystal packing of 1D and 2D "metal-4,4`-bipyridine" coordination polymers has been addressed in terms of structural analysis and fluorescence spectroscopy. The phenomena of supramolecular isomerism resulting from the use of metal-carboxylate clusters as building blocks for a variety of metal-organic materials will be discussed. Finally, an analysis of the Host:Guest and suprasupermolecular properties of discrete nanostructures will be provided.
Thesis:
Dissertation (Ph.D.)--University of South Florida, 2008.
Bibliography:
Includes bibliographical references.
System Details:
Mode of access: World Wide Web.
System Details:
System requirements: World Wide Web browser and PDF reader.
Statement of Responsibility:
by Gregory J. McManus.
General Note:
Title from PDF of title page.
General Note:
Document formatted into pages; contains 134 pages.
General Note:
Includes vita.

Record Information

Source Institution:
University of South Florida Library
Holding Location:
University of South Florida
Rights Management:
All applicable rights reserved by the source institution and holding location.
Resource Identifier:
aleph - 002001124
oclc - 319618224
usfldc doi - E14-SFE0002596
usfldc handle - e14.2596
System ID:
SFS0026913:00001


This item is only available as the following downloads:


Full Text
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ABSTRACT: The interest in metal-organic materials namely, coordination polymers and metal-organic frameworks has risen dramatically over the past few years. To a certain extent this interest is a consequence of the realization chemists have discovered how to play a form of molecular Lego in which metal cations or metal clusters represent the bricks (or nodes) and organic ligands such as 4,4-bipyridine (bipy) or benzene-dicarboxylate represents the glue (or spacers). The "node-and-spacer" approach to self-assembly can be invoked in such a manner that a plethora of infinite architectures and discrete polyhedra can be generated from geometric principles, some of which are unprecedented in either natural or synthetic materials. The research presented within this dissertation primarily involves the use of coordination chemistry and supramolecular chemistry in the context of synthesizing metal-organic materials and deals with how subtle variations in reactants and procedures can have dramatic effects upon the materials formed. The effect of aromatic guest molecules on the crystal packing of 1D and 2D "metal-4,4`-bipyridine" coordination polymers has been addressed in terms of structural analysis and fluorescence spectroscopy. The phenomena of supramolecular isomerism resulting from the use of metal-carboxylate clusters as building blocks for a variety of metal-organic materials will be discussed. Finally, an analysis of the Host:Guest and suprasupermolecular properties of discrete nanostructures will be provided.
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PAGE 22

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60 &13; 4!<6rr=$r$> 13; 4!<6?rr= nnn&n0'FnGn-#9;;$ nrnrnrn#*;C$ rn/rnrnr r%*=n&n@2'rr '6nrnrr %9nnr# rn@6@ rrnn n2n@2' %*=rnrn &nnrr$rn nrnnn %*=nnrrnnnn& n)nrr nrnrnrrn P9'#%8$'Q FnG#n-$nnrrnr nFn! nGrnrrnP9'#%8$'QFnG# $ @( !, . 5 +. '( 2( ( ,+' +' A 2 5 ( ;,. '+ ;' r ) r! (,' <+ ( %& B;. n ). % +( ( ((

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8" n&n-#6'$18 rnrrr nr/nrn&nr nnnrnr rnr!6!n&n#$r rr-r/nrnn n'";rnnrn rn rnnnr/nrnnrr rr Hnn!n&nnr+n$ = nP%'#rn$'#<'$'Qr&nn-r,$'=9!'nn rP%'#8! $'#<'$'Q,$6=
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8' nrrn&P8Qn+n$ #$nn,$'!nn,n$6!n n r!rnnrnr nnnnnrn &rnn
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88 ( %rnr ( +n$n'=nnr#$ nrrr/n*;C.rn'=nn r,$rnr ( rrn(nn6!n nn! n&nrr#n&nnrn n& n$,$););n-n nrrn!n&r #nrn( nnrrn&n nrn( nnrrr$ nr ( rnr" nrr 8!&n&nn ( n ( '=rr rn-n););nnnI!n&rr nrnrr 6!nn*;Crn(nn nrnnr"0 ( nrnr"10 ( =rrr rnrnrrnn*;C nrnrrnr r (

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82 + %rnr + +n$rrnn#n&n'! nrnn& n$, $)))n-nnrrn&!n&r (n % + OPI'#$'#'!$'Qb'Rrrr nn*;Crr!nrrnn rr#6>$ nnn#nr r rnrnrn ?r nrnnr r$r"1@nr "0#nrn( nnr2!r rnrnrn n nnn rn6!r nn'!n&nnr$ rrn nrrnnnn rrrn-r))) n&!n&rrnnnrrr nnn rnn "@

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8@ %rnr ,C n$rrnn #n&nnrnn& n$, $););n-nnrrn&!n&r nnnrr + rnrnrrnn&n>2%rrrr rrn'! n&nnr)n nrr rnPI'#$'Qnnnnrrrnn nnr nrnn&n6""%r !2$0 %r ,& OPI'#$'#:$'Q8R#60$#:U8! n , 62! n ,r ,8!& nr/ ,& $r r'!nn*;Crnrr nrrnr *;Crnrnnrr + ,r n ,& , ,n n rr nnnfI!nnrn-n);); nrn&!n&r nrnnrn"18"' n&nn n

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8> %rnr -C n$rr'!nn #n&nnrnn& n$, $nLnrr-nnnr rn))) n-n&!n&r nnnrr rnrnrrnn&n '""%rrrr !rr n8!n&nnr nn nrr ,& rnrn rrnn&n'2"%rrrr rrnr/n& nnr)n nrrr n ,& rnPI'#$'Q '!nnnnrrrnn nnrnrn n&n62"%r -r nrrnnn rnnrrn nrrrnrn B6!nnnn rnr2!! !6!n&n''@n '!nnnnrnrn 2!&!!6!

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80 n$6!nn#6!n$,$ nn&nr6!nr ,$ nn&nr6!nr n&n''>n2!n!!6!n&n''03nrn nnn'!nnnnrn n2!r!! 6!n&nrrn% OPI'#2!*6!$'#/$'Q'!b 'PnQLb'/b ( R#61$rrr -r&nnnnn r nn n-rnnrrn rn'=nr rn-nr)))nrn nrnn2> rrrrnnrr rn&nr nrnn r nnr r'=nnrrn nnnnn&n nrr*;C.r n rnrn!n&nrrn r!'2!n&n1" '82@!!6!n&n''1nnn'6"< rnnnrrnn-r 6!nn#6!n$#6 1n$6!nn&nrn

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81 %rnrr n +n$r/n*;Cr rnr ,$'=rnn r ,4n$r/n*;Crrnr .D $'=rnnr .nnr6nnnr #61$n #61$nrn r n r % OP%'#6!n$'#8!&$'QbR# 6n!$rrrr/n*;Cn -n rr n6!nnrnr '= nnrrn-nrnr n&!n&rnn rnnr""% P%'#6!n$'#8!&$'Q# 6!$rrrr/n*;Cn -n rr n6!nnrnr '=nn rrn-nrnrn &!n&rnnrnnr '@

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2" Snn+n$'=nSn#$nrr nn*;C.rn'=Snr,$ Snn nrrrnnr,$r nr #n&nnrnn &n $EFG34567 % OPI'#$'#8!&$'QbnR rr r!nrrnn*;Crn'=rr rrnrn nrn&nnSngn'6)Sngnrnr!rn nrrnnr nr n&nr nSngnr'6'!'68nnr&n n nrnSngnnr%#$*;C'6@!'6>I#$rrn I'rnrnnrnn

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28 ( rn8!r/nnn r+n$r/n,$,$%*8,$ 3rnrnrnrr nnrr r/nnnrrn'=r/nr &rrnn6=rnnr/nnn rnrnr nrrnr%*8n/nn#6@$ & nr;n'60nfn1"nn -r rr/nnnr r@20 n rr&nrnrrnn8! )r nrnr&rrrn nnrnn rnrnrrnn n3nrn rrrn rnnr

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22 rnrrnr&n r@20 rrn rnr%*8nrrrrrrnrn r-r nnrn r rrnn *h#&$n'61nrn&n#@@@ @@'i$r *hn%*8nr nr#@'@'@6@6@'i$ r nrrrrnrr nnnr nrrnrnn nrnnn nFr!Gnnrn)rrnr F@'Grrnrnnr& rrnnr nnrF@6Grnrr& r FiGrrrnrrn rnrrnrn rrr&rr nrnnr n-rn rrr rnnnr r--rr8! r/nnnr nnnrr rnrnrrnn&n'2"% rrrr/ n&nnr% nnrnrnn&n 62"% rrn&&nrnnr rnrnnn n!nnr#'=nn rr'=Sngrrn6= C*!$nnrnr r/n-rrnnnrn* nnnrrr

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2@ nrnnrrr nnnSngrrn nnnrnr rnn%#$ nI#$nnrnn rrnrrrn nnnrn& nnnnn nrn-rnr rnr ("#8r )nnrrnr,rr nn rnnr &0123r43r4679:3(4 %rrrnr ( nnrn62Mr rnnnn r#"":$!6!n&n #0'"81$n#$ n&nn#2""2"$n nn#"":$n nr#"":$#"': @$n#'":$ &0123r43!#r46797:3(4 % ( nrrr&nnr #'"":$! 6!n&n#8'"'2$n #6""'8$#$ n&nn#2""2"$#'" :$n8!& #"':'"$6rn>"%%rrrnrnn rnrnrn n

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