%LJJHU'1$1HZ'RXEOH+HOL[ZLWK([SDQGHG6L]H
$QGUHDV0DU[DQG'DQLHO6XPPHUHU
%HVLGHVLWVLPPHQVHELRORJLFDOLPSRU WDQFH'1$LVEHFRPLQJDQLQFUHDVLQJO\
LQWHUHVWLQJ WDUJHWIRUFKHPLFDO PRGLIL FDWLRQV 7KHVH HIIRUWV DUH GULYHQ E\
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
SURSHUWLHV
5HFHQWO\.RRO DQG FRZRUNHUV GH VFULEHG D QHZ V\VWHP LQ ZKLFK WKH XQPRGLILHG'1$EDFNERQHLV PDLQ WDLQHG EXWWZRRI LWVQXFOHREDVHVDUH UHSODFHG E\ H[WHQGHG DQDORJXHV<- 7KH DQDORJXHV ZHUHGHVLJQHGE\ IXVLQJ D EHQ]HQH ULQJ EHWZHHQ WKH :DWVRQ
&ULFNUHFRJQLWLRQVLWHV DQGWKHFRQQHF WLRQ RI WKHQXFOHREDVHWR WKH VXJDU PRLHW\7KLVLQVHUWLRQUHVXOWVLQD
$
VL]HH[SDQVLRQDQGFRQYHUWVWKHELF\FOLF SXULQH$LQWRWKHWKUHHULQJV\VWHP[$
DQGWKHF\FOLFS\ULPLGLQH7LQWRELF\
>- 3ULYā'R]'U $0DU[
'LSOā&KHP' 6XPPHUHU
.HNXOāOQVWLWXWI2U 2UJDQLVFKH&KHPLH XQG %LRFKHPLH
8QLYHUVL8LW %RQQ
*HUKDUGā'RPDJNā6WUDVVH %RQQ *HUPDQ\
)D[(āPDLODPDU[#XQLāERQQGH
>-:H WKDQN(7.RRO 6WDQIRUGIRUNLQGO\
SURYLGLQJWKHFRRUGLQDWHVRI'1$DQG ['1$GXSOH[HV
FOLF[7 6LQFH WKLV WUDQVIRUPDWLRQGRHV QRW DIIHFW WKHK\GURJHQERQGLQJVLWHV .RROHWDO UHDVRQHGWKDWDUWLILFLDO VH TXHQFHVFRQWDLQLQJ WKHVH EDVHV VKRXOG IRUP DGRXEOH KHOL[ZKHQ FRPELQHG ZLWK '1$ FRQWDLQLQJ FRPSOHPHQWDU\
QXFOHRWLGHEDVHV7KHZRUNZDVLQVSLUHG E\ZRUNRI/HRQDUGHWDO ZKRXVHG[$
WRSUREH$73GHSHQGHQWHQ]\PHVWKUHH GHFDGHVDJR- )URPWKHPRGLILHGEDVHV [$ DQG [7 .RRO HWDO V\QWKHVL]HG WKH QXFOHRVLGHDQDORJXHVG[$DQGG[7DQG
G[7
$ā 7 $āāā7
.H\ZRUGV
'1$ā'1$VWUXFWXUHVāIOXRUHVFHQFHā ROLJRQXFOHRWLGHVVXSUDPROHFXODUFKHPLVWU\
ZHUH DEOH WR LQFRUSRUDWHWKHP LQWR ROLJRQXFOHRWLGHVDQGVWXG\WKHLUSURSHU WLHV7R HOXFLGDWH ZKHWKHUWKHH[WHQGHG DQDORJXHV IRUP :DWVRQ&ULFN EDVH SDLUV LQ DQXQPRGLILHG'1$HQYLURQ PHQW .RRO HWDOLQYHVWLJDWHGGXSOH[HV FRQWDLQLQJVLQJOHH[WHQGHGEDVHV[$RU [7QHDU WKHPLGGOH RI D EDVHSDLU ROLJRQXFOHRWLGHLQ)LJXUH7KH\
IRXQGWKDWERWKDQDORJXHVZKHQ SDLUHG WRWKH XQPRGLILHG SDUWQHUGHVWDELOL]H
WKHGRXEOH KHOL[UHODWLYHWRWKH XQPRGLILHG GRXEOH KHOL[
7KURXJKLQYHVWLJDWLRQRIQXFOHR EDVHYDULDWLRQVRSSRVLWHWKHH[
WHQGHGDQDORJXHVLWEHFDPHDS SDUHQW WKDW[$ KDV D VOLJKW SDLULQJVHOHFWLYLW\ IRU 7 RYHU
&* RU $ DQGWKDW[7LQ LV PRUH XQVHOHFWLYH LQSDLULQJ WR LWV SDUWQHU LQ WKH RSSRVLWH VWUDQG RI WKH GXSOH[ 7KHVH REVHUYDWLRQVLQGLFDWHWKDW WKH '1$ EDFNERQH LV WRR ULJLGWR WROHUDWHDOWHUDWLRQVVLQFHVLJQLI LFDQWGLVWRUWLRQRIWKHKHOLFDO FRQIRUPDWLRQ ZRXOG EH UH
$7 $āāāā7 [$7 [7$ [7$
*āāāāā& *āāāāā& 7[$ [7$ [$$
$āāāā7 $āāāāā7 [$7 [7$ 7[$
$āāāā7 $āāāāāā7 [$7 [7$ [$$
[$1 1[7 7[$ [7$ 7[$
*āāāāā& *āāāāā& [$7 [7$ [$$
$ā 7 $ 7 7[$ [7$ [7$
$āāāā7 $āāāāāā7 7[$ [7$ 7[$
$āāāā7 $āāāāā7 [$7 [7$ [$$
$āā7 $āāāāā7 7[$ [7$ $[7
*& *āāāāF
)LJXUH6HOHFWHG '1$ DQG H[WHQGHG'1$ ['1$FRQVWUXFWVOOO$OO['1$VWUXFWXUHVZHUHFRP SDUHGZLWKFRUUHVSRQGLQJ'1$VWUXFWXUHVFRQWDLQLQJH[FOXVLYHO\QDWXUDOEXLOGLQJEORFNV&RQā VWUXFWVDQG H[KLELWGHFUHDVHGDQG LQFUHDVHGGXSOH[VWDELOLW\ZKHQ FRPSDUHG ZLWKWKH VWUXFWXUHVPDGHXSRIQDWXUDO EXLOGLQJEORFNV
First publ. in: Angewandte Chemie International Edition 43 (2004), 13, pp. 1625-1626 DOI: 10.1002/anie.200301737
Konstanzer Online-Publikations-System (KOPS) URN: http://nbn-resolving.de/urn:nbn:de:bsz:352-opus-131193
URL: http://kops.ub.uni-konstanz.de/volltexte/2011/13119/
TXLUHG WRDFFRPPRGDWH WKH H[WHQGHG EDVHDQDORJXHV ZLWKLQ DUHJXODU '1$
KHOL[
.RRO HWD, VSHFXODWHG WKDWDKHOL[
H[FOXVLYHO\FRPSRVHGRXWRIWKHH[WHQG HGQXFOHRWLGHV ZRXOG FLUFXPYHQW WKH JHRPHWULFFRQVWUDLQWV GLFWDWHG E\ WKH UHJXODU'1$KHOL[7KXVDVHOIFRPSOL PHQWDU\ ROLJRQXFOHRWLGH ZDVLQYHVWL JDWHG WKDW IRUPHG D KHOL[ ZLWK DQ H[SDQGHG QXFOHRWLGH LQ HYHU\ VLQJOH EDVHSDLU7KH\IRXQG WKDWWKLV[$UHVL GXHFRQWDLQLQJFRPSOH[LVPRUHVWDEOH WKDQ WKH QDWXUDO GXSOH[ E\ NFDO PRO,7RWHVW WKHVHTXHQFHJHQHUDOLW\
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
6WUXFWXUDO DQGWKHUPRG\QDPLF LQ YHVWLJDWLRQVLQGLFDWHRQO\ VPD,,FRQIRU PDWLRQDOFKDQJHVLQWKH '1$VXJDU SKRVSKDWH EDFNERQHDQG VXJJHVWWKDW WKH ODUJHUGLDPHWHURIWKH ['1$KHOL[
UHVXOWVLQDJUHDWHUQXPEHURIEDVHVSHU
21$ ['1$
)LJXUH6LGHYLHZ RI2āEDVHāSDLU'1$ DQG PRGHOHG['1$GXSOH[HV 6KRZQ DUH WKH&RQ QROO\VXUIDFHVZLWK FDYLW\GHSWKGHSHQGHQWFRO RULQJEOXHVKDOORZ JUHHQ GHHS7KHVWUXF WXUHVZHUH JHQHUDWHGZLWK WKH6<%</
75,326VRIWZDUH SDFNDJH
WXUQWKDQLQ%'1$$GGLWLRQD,,\VL]H H[WHQVLRQPLJKWFDXVHWKH PLQRUDQG PDMRUJURRYHVRIWKH['1$KHOL[WREH ZLGHUWKDQWKRVHRI%'1$
7KH GHYHORSPHQWRI ['1$ LV DQ RXWVWDQGLQJ DQGYHU\ HOHJDQW H[DPSOH IRUD VXFFHVVIXO PROHFXODU GHVLJQ7KH UHSRUWE\.RROHWD,SRLQWVRQFHDJDLQDW WKH JUHDW SRWHQWLDORIQXFOHLFDFLGVDV VXLWDEOH VFDIIROGV IRUQDQRVFDOH HQJL QHHULQJ3@ 7KHHQODUJHG ROLJRQXFOHRWL GHVKDUERUIHDWXUHVQRWIRXQGLQQDWXUDO '1$2ZLQJWRWKHLQFRUSRUDWLRQRIWKH IOXRUHVFHQW PRQRPHUV[$ DQG [7WKH QXFOHRWLGHV G[$DQG G[7DUH KLJKO\
IOXRUHVFHQWDV DUHWKH UHVXOWLQJROLJR QXFOHRWLGHV7KXVLQ['1$DOOWKHEDVH SDLUVDUHIOXRUHVFHQWJLYLQJ DSRO\PHU ZLWK KLJK IOXRURSKRUH GHQVLW\ .RRO HWD, VSHFXODWH WKDW WKLV SURSHUW\RI ['1$ FRPELQHG ZLWK LWV LQFUHDVHG ELQGLQJSURSHQVLW\PLJKWEHSDUWLFXODUO\
XVHIXOIRU DSSOLFDWLRQVLQGHWHFWLRQDQG GLDJQRVLVRI'1$RU 51$ )RUWKLV SXUSRVHDVZHOODVWRFRPSOHWHWKHVL]H H[WHQGHG JHQHWLF DOSKDEHW WKHWRGDWH PLVVLQJ QXFOHREDVHVXUURJDWHV [* DQG [&DUHDZDLWHG7KHLUSUHSDUDWLRQPLJKW
HQDEOHIXUWKHUVL]HH[SDQVLRQIRUH[DP SOH WKURXJKFRQVWUXFWLRQ RI D KHOL[
FRPSRVHGH[FOXVLYHO\RIVL]HH[WHQGHG QXFOHRWLGHV $ IXUWKHU LQYHVWLJDWLRQ ZRXOGEHWR VHH LI '1$ SRO\PHUDVHV SURFHVV WKH H[WHQGHG DQDORJXHV $V QRWHG E\ .RRO UHFHQWO\>@ WKHVH DQD ORJXHV PLJKW EH XVHIXO WR WHVW WKH K\SRWKHVLVRIDFWLYHVLWHWLJKWQHVVIRU '1$ SRO\PHUDVHV 7KLV PRGHO LV SUR SRVHGDV DQ H[SODQDWLRQIRU HQ]\PH VHOHFWLYLW\DQGLWVYDULDWLRQDPRQJVHY HUDO '1$ SRO\PHUDVHV-@ :H DZDLW IDVFLQDWLQJSURJUHVVDORQJWKHVHOLQHVLQ QHDUIXWXUH
>@ 5HYLHZVD$'H0HVPDHNHU5+DQHU 3 0DUWLQ+ 0RVHU$FF &KHP5HV
E<6 6DQJKYLLQ '1$DQG$VSHFWVRI0ROHFXODU%LRORJ\
(G(7 .RRO3HUJDPRQ2[IRUG FKDS F6 9HUPD) (FNVWHLQ
$QQX5HY%LRFKHP
G/: 0F/DXJKOLQ0:LOVRQLQ'1$
DQG $VSHFWVRI0ROHFXODU%LRORJ\(G (7 .RRO 3HUJDPRQ2[IRUG FKDSH1& 6HHPDQ1DWXUH I&01LHPH\HU 0
$GOHU$QJHZ &KHP $QJHZ&KHP,QW (G J$ 0DU[,'HWPHU
*DVWHU'6XPPHUHU6\QWKHVLV
>@5HYLHZVD(7 .RRO& 0RUDOHV . 0 *XFNLDQ $QJHZ &KHP $QJHZ &KHP,QW(HO E(7.RRO$FF
&KHPRe~~ F+$
:DJHQNQHFKW$QJHZ&KHP $QJHZ &KHP ,QW (HO
>@+/LX*DR6 5/\QFK<'6DLWR/
0D\QDUG(7.RRO6FLHQFH
>@ D1/HRQDUG 0$6SUHFNHU $*
0RUULFH- $P &KHP 6RF E5 $ /HVVRU.-*LEVRQ1- /HRQDUG%LRFKHPLVWU\
>@ (7.RRO$QQX5HY%LRFKHP