殐 殐 27 1 Vol.27 No.1 2009 1 ImagingScienceandPhotochemistry Jan.,2009 檭檭檭檭檭檭檭檭檭檭檭檭檭檭殐 殐 2+ HIJKLMN! 犉犲 / 3+ 犉犲 O 1,2, (1. 1,2,!" 1,2,#$% 1,2,&' 1!"#,)*100190;2.!"+,)*100049) $ %:* GHI J'(E) 4 (4 (2 (2 K)LM )N ) 2, 2 :6,2 O 犔. Fe 2+ Fe 3+ P+, 犔 4Q(ORST*LU V WE 1 20)XY- B Y Y* Y,D Z[ \ 374*574nm]^_G `.a,bc 2+, 犔 Fe 2+ Fe 3+ 2 ^] 9* 9., 犔 Fe 2+ Fe 3+ 2 + 9 * 8 (LOD). & ' :EY;J ;O ';Fe 2+ ;Fe 3+ :1674 0475(2009)01 0008 08 ()* :O64 +,-.:A Y, +W,3 ;L-;392 T./0 1. Z 2,3 I+1, = 2 L+1 3 4R [1]. ^, ; Fe 2+ L Fe 3+ Z CH9 I [2] ;J [3 5] L< [6]., 5 ' 6 ; 7 8 L,3 L c cd.9 8 L,3 I+1 G 8 : #R W, T ; ;BC '.BCP. [7] L. I 3 SB 3J [8], 2 7..M, T 3 01 (E) 4 (4 (2 (2 ) )! ) 2,2 :6,2 1 <= 犔. Fe 2+ L Fe 3+ 3 @, 01 犔. @ 2 L>.? HI @A B3, 犔,3 ; C C.,I D E, @ 374L574nm ; 3 DL Fe 2+ /Fe 3+ I ] cdl 0 cdc W. /01 :2008 05 16; 1 :2008 06 13. S: F,E mail:fuwf@mail.ipc.ac.cn. 2: ] (90610034L20671094). 3456:G H (1974 ),,!"+,Z B&'!". 8
1 G H : 1 <=I+1 Fe 2+ /Fe 3+. 9 1 1.1 89:; # L45D2 \.2 J,2 <=LKLM/0N Alfa (. 1! M # "!"J O/ */ 8 8 0 1 " L H2O2 D2 )* N 9:.NBSLBPO ^. "!L) + P; La.]3 9:. 01 犔 Q c D 7.0 10-5 mol/l (1 " L # Q 1 20). RJ B3 01 @2 Fe(NO3) 3 Fe(ClO4) 2 Cu(ClO4) 2 LiClO4 NaClO4 KNO3 Ni (NO3) 2 Pb(NO3) 2 Co(NO3) 2 Zn(ClO4) 2 MgSO4 CdSO4 MnSO4 Hg(OAc) 2 CaCl2. TDQ cd 2.0 10-3 mol/l. Fe(NO3) 3 L Fe(ClO4) 2 RJ 0 1 L, 1 10,S <Y1μL; 11 R 15,S <Y2μL;= S <Y4μL9 T. H9 I HitachiModelU 3010 DN;W. HitachiModel F 4500 A;W. 8C Bruker400MHzAVANCE I;W.ESI APEXIModelFT ICR A;W. CarloErba1106UV \A UV \. 1.2 O 犔! 01 犔 WX0 L F 1#.Y, [9,10]. @0 (1 01 犔 0 Thesynthesisrouteofcompound 犔 011L2(I 1).,I, 012(0.305g,0.66mmol)L2 J(0.0686g,0.44mmol)<Y "!(100mL),( Z [\20min <Y NaH(0.02g,0.83mmol),<]U^_ c12h.`a (, _B bc 1, # (3 1mL),: ]3 (3 1mL). I J50 @ 4h,b # B c 1 犔, >73.3 %. 1 H NMR (400MHz, CD3OD):δ=7.32 (s,1h,ethylene H),7.35 (s,1h,ethylene H),7.37 (m,2h, Py H),7.47 (m,2h,2 naphthalene H),7.69 (d,2h,benzene H),7.78 (d,2h, benzene H),7.79(d,1H,2 naphthalene H),7.82(t,2H,Py H),7.89(d,2H,2
10 27 naphthalene H),7.95 (d,2h,2 naphthalene H),8.68 (d,2h,py H),8.75 (d, 2H,Py H),8.79(s,2H,Py H);ESIMS: 犿 / 狕 =462.4(M + +1).C33H23N3(461.4) UV \ ; :C85.72%,H5.01%,N9.05%;N :C85.87%,H5.02%,N9. 10%. 2 2+ 3+ 2.1 犔 犉犲 : 犉犲 -! P Fe 2+ LFe 3+ 3 @RJ 01 犔,=!",3., H9 I -;( 2L3# ). (2 Fe 2+ 3 RJ 01 犔 H9 G : 01 犔 I574nm D < [Fe 2+ ] ChangesinUV visspectraof 犔 insolutionuponprogressiveadditionoffe 2+ Theinsetshowstherelationshipbetweentheabsorbanceof 犔 at574nmandtheincreasing[fe 2+ ] 2 =, Fe 2+ 3 <Y, 01 犔 I374L574nm @ 3, DD c A. 9,. 2. 01 犔 I374nm B Fe 2+ L1 <=Q G< $R(intramolecular charge transfer:π π tpy,ε=3.63 10 4 L mol -1 cm -1 ). 3 = B B#Q < $R(metal to lig and charge transfer,mlct) [11]. G #, <Y Fe 2+ L 犔 1 2, D b,, 8. Fe( 犔 ) 2+ 2 (εfe( 犔 ) 2+ 2 =2.50 10 4 L mol -1 cm -1 )Q01. RJ, 8@, ' J 犔 Fe 2+ 0 [12]. 9, =8@, 01 犔 I574nm D A L<YFe 2+ cdi0 2.8 10-5 mol/l 5GBC W. 0B
1 G H : 1 <=I+1 Fe 2+ /Fe 3+. 11 09 : 犃 =0.03042[Fe 2+ ]+0.00665, 犚 2 =0.99856.LOD=8.0 10-7 mol/l, L 2. ' 3 [1,8,13].LOD2J < 3σ c 3 cd [13]. 3, Fe 3+ <Y, 01 犔 H9 I374(ε=3. 82 10 4 L mol -1 cm -1 )L574nm 3, D + c A. 01 犔 I374nm BL Fe 2+ RJ, 3 (3 Fe 3+ 3 RJ, 01 犔 H9 G : 01 犔 I574nm D < [Fe 3+ ] ChangesinUV visspectraof 犔 insolutionuponadditionoffe 3+ Theinsetshowstherelationshipbetweentheabsorbanceof 犔 at574nmandtheincreasing[fe 3+ ] '2 Fe 3+ LQ 0 + : c [6,14],+ Fe 2+, Fe 2+ + MLCT. \G =,Fe 3+ L 犔 0 L Fe 2+ 犔,D2. 1 2 Q01,?. Fe( 犔 ) 3+ 2 (εfe( 犔 ) 3+ 2 =1.96 104 L mol -1 cm -1 ).,RJ T Y.8@ >,. N 0. 9, 01 犔 I574nm DL<Y Fe 3+ cdi0 3.5 10-5 mol/l C W. 0B 09 : 犃 =0.01751[Fe 3+ ]-0.00454, 犚 2 =0.98742,LOD=4.1 10-6 mol/ L. T!" 犔 0 Fe 2+ Fe 3+., 7 UV vis -;(I 4). 0 Fe 2+ Fe 3+ cd 2.0 10-3 mol/l,s R< 0 Q :2μL 4μL 6μL 8μL 10μL 12μL 14μL,DR<7. =, RJ L P Fe 2+ RJ #B &; 9 2, 8I L 犔 0,Fe 2+ ' Fe 3+.G @ 犔 I574nm DL<Y,3 cdi0 4.2 10-5 mol/lc W. 0B 09 : 犃 =0.02094[Fe 2+ +Fe 3+ ]-0.0084, 犚 2 =0.99786,LOD=2.9 10-6 mol/l.
12 27 2+ 3+ 2.2 犔 犉犲 : 犉犲!QRP- :STUP- 01 犔 ( 犮 L=7.0 10-5 mol/l)l Fe 2+ /Fe 3+ L 犔. Q01 ( 犮 Fe( 犔 ) 2+ = 犮 2 Fe( 犔 ) 3+ 2 =3.5 10-5 mol/l)i I bbc ( 犔 :. ;Fe( 犔 ) 2+ 2 :2 ;Fe( 犔 ) 3+ 2 :> ), 5 I T (I 5a). =,Fe( 犔 ) 2+ 2 L Fe( 犔 ) 3+ 2 I350 490nm DC3, DI374 nm. Fe( 犔 ) 3+ 2 I DD Fe( 犔 ) 2+ 2. 9,I490 700nm 5G,Fe( 犔 ) 3+ 2 D. E BE Q01 C @, (4 Fe 2+ LFe 3+ 3 0 RJ 01 犔 H9 G : 01 犔 I574nm D < [Fe 2+ +Fe 3+ ] ChangesinUV visspectraof 犔 insolutionuponadditionofthemixtureoffe 2+ andfe 3+ Theinsetshowstherelationshipbetweentheabsorbanceof 犔 insolutionat574nm andtheincreasing[fe 2+ +Fe 3+ ] 6 T. 01 犔,3 C, 5(b)#. @<Y B3, 犔 DCCI574nm (<YCo 2+,I520nm ), CFe 2+ Fe 3+ 狀 <Y. 9,I B3 (M + ) HI,a Ni 2+ Cu 2+ =9, Fe 2+ 3, 01 犔 (I 5c); Fe 3+ 3, Ca 2+ Li + Na + K + Mg 2+ Mn 2+ Pb 2+ HI 犔 @ + @A(I 5d).,I 01 犔, < (donor) 2 L < (acceptor) 1 <= D D :I (spacer)!. 7 D S A D F B B 3 L 0, 3, < ' C D., 01 犔 = + D G< $R(ICT). ICTL + = + R, 1., = [15]. 9, 1 <= 1 Q =L B3 0, BC 0 [16], 2 0=,' I I b(>400nm) + MLCT C,3 L 3
1 G H : 1 <=I+1 Fe 2+ /Fe 3+. 13 [12]. Co 2+ L 犔 0,Q01 λmaxi520nm.= E 0 B 01 犔 ',3 E 8 LL B 3. (5 (a) 犔,Fe( 犔 ) 2+ 2 LFe( 犔 ) 3+ 2 H9, G : 犔 Fe( 犔 ) 2+ 2 Fe( 犔 ) 3+ 2 ; (b)<y B 3 (3.0 10-5 mol/l), 犔 H9 ; (c) <Y B3 (3.0 10-5 mol/l), <YFe 2+ (3.0 10-5 mol/l), 犔 I574nm D ; (d) <Y B 3 (3.5 10-5 mol/l), <YFe 3+ (3.5 10-5 mol/l), 犔 I574nm D (a)thecomparisonofuv visspectraof 犔,Fe( 犔 ) 2+ 2 andfe( 犔 ) 3+ 2 insolution Inset:thecomparisonofcolorsofsolutionsof 犔,Fe( 犔 ) 2+ 2 andfe( 犔 ) 3+ 2 ; (b)changesinuv visof 犔 insolutiononadditionofdiferentmetalcations(3.0 10-5 mol/l); (c)changesinabsorbanceintensityof 犔 insolutionat574nmonadditionofothermetalcations (3.0 10-5 mol/l)andsubsequentadditionoffe 2+ (3.0 10-5 mol/l); (d)changesinabsorbanceintensityof 犔 insolutionat574nmonadditionofothermetalcations (3.5 10-5 mol/l)andsubsequentadditionoffe 3+ (3.5 10-5 mol/l) 3 0 3 =1 <= <,2 <,BCdonor spacer
14 27 acceptord F 01 犔. LFe 2+ LFe 3+. Q01 =, IH9 I E @I374L574nm. 9,I @A B 3 HI, 犔 E,3 BC @'. 9, 犔 I 574nm DLFe 2+ Fe 3+ T 01 @I0 2.8 10-5 mol/l,0 3.5 10-5 mol/ll0 4.2 10-5 mol/lcd 5GC W. 犔 Fe(I) Fe(I) LFe(I+ I) LOD @28.0 10-7 mol/l 4.1 10-6 mol/l 2.9 10-6 mol/l. 5 8 01 犔 BCc +W,3 ;.. FG +: [1] PulidoTP,BarreroMJM,PérezCMC.Aflow throughfluorescentsensortodeterminefe(i)andtotalin organiciron[j]. 犜犪犾犪狀狋犪,2000,51:537 545. [2] PehkonenS.Determinationoftheoxidationstatesofironinnaturalwaters[J]. 犃狀犪犾狔狊狋,1995,120:2655 2663. [3] PicardV,EpsztejnS,SantambrogioP,CabantchikZI,BeaumontC.Roleofferitininthecontrolofthelabile ironpoolinmurineerythroleukemiacels[j]. 犑. 犅犻狅犾. 犆犺犲犿.,1998,273(25):15382 15386. GrabchevI,ChovelonJM,QianX H.Apolyamidoaminedendrimerwithperipheral1,8 naphthalimidegroups capableofactingasapetfluorescentsensorformetalcations[j]. 犖犲狑犑. 犆犺犲犿.,2003,27:337 340. GrabchevI,ChovelonJM,PetkovC.Aniron(I)selectivedendritechelatorbasedonpolyamidoamineden drimermodifiedwith4 bromo 1,8 naphthalimide[j]. 犛狆犲犮狋狉狅犮犺犻犿犻犮犪犃犮狋犪犘犪狉狋犃,2008,69:100 104. [4], +,,. : SchifQ B3!"[J]., 2008,26:109 115. YuTZ,DingXS,ZhaoYL, 犲狋犪犾.Studyontheinteractionoftransitionionswithaopen chaingrownether schifbase[j]. 犐犿犪犵犻狀犵犛犮犻犲狀犮犲犪狀犱犘犺狅狋狅犮犺犲犿犻狊狋狉狔,2008,26:109 115. [5],G H, 8,. = '!"[J].,2008,26: 25 31. LiJZ,WangJ,ChiSM, 犲狋犪犾.Thesynthesisandstudyofnovelwater solublepamnderivativesasfluorescent probematerials[j]. 犐犿犪犵犻狀犵犛犮犻犲狀犮犲犪狀犱犘犺狅狋狅犮犺犲犿犻狊狋狉狔,2008,26:25 31. [6] WansapuraCM,SeliskarCJ,HeinemanW R.Spectroelectrochemicalsensingbasedonmultimodeselectivity simultaneouslyachievableinasingledevice.20.detectionofmetalionsindiferentoxidationstates[j]. 犃狀犪犾. 犆犺犲犿.,2007,79(15):5594 5600. SuganandamaK,SanthoshP,SankarasubramanianM,GopalanA,VasudevanT,LeeKP.Fe 3+ ionsensing characteristicsofpolydiphenylamine electrochemicalandspectroelectro chemicalanalysis[j]. 犛犲狀狊狅狉狊犪狀犱犃犮狋狌 犪狋狅狉狊犅 : 犆犺犲犿.,2005,105(1):223 231. [7] WolfbeisOS.Materialsforfluorescence basedopticalchemicalsensors[j]. 犑. 犕犪狋犲狉. 犆犺犲犿.,2005,15:2657 2669. [8] AbbaspourA,MehrgardiMA,NooriA,KamyabiMA,KhalafiNA,RadM NS.Speciationofiron(I),iron (I)andful rangephmonitoringusingpaptode:asimplecolorimetricmethodasanappropriatealternativefor optodes[j]. 犛犲狀狊. 犃犮狋狌犪狋狅狉狊犅 : 犆犺犲犿.,2006,113(2):857 865. LiangZQ,WangCX,YangJX,GaoH W,TianYP,TaoXT,JiangM H.Ahighlyselectivecolorimetric chemosensorfordetectingtherespectiveamountsofiron(i)andiron(i)ionsinwater[j]. 犖犲狑犑. 犆犺犲犿., 2007,31:906 910. [9] KrohnkeF.Thespecificsynthesisofpyridineandoligopyridines[J]. 犛狔狀狋犺犲狊犻狊,1976,1:1 24. [10] ChenY,ZhaoXJ,ZhangJF,FuWF.Synthesisofanew2,2':6',2' terpyridinederivativeanditscoordination
1 G H : 1 <=I+1 Fe 2+ /Fe 3+. 15 property[j]. 犆犺犻狀. 犆犺犲犿. 犔犲狋.,2007,18:530 532. [11] Meier M A R,SchubertU S.Fluorescentsensingoftransition metalionsbasedontheencapsulationof dithranolinapolymericcoreshelarchitecture[j]. 犆犺犲犿. 犆狅犿犿狌狀.,2005,36:4610 4612. [12] DobrawaR,LysetskaM,BalesterP,Grü1neM,Wü1rthnerF.Fluorescentsupramolecularpolymers:metal directedself assemblyofperylenebisimidebuildingblocks[j]. 犕犪犮狉狅犿狅犾犲犮狌犾犲狊,2005,38:1315 1325. [13] OterO,ErtekinK,KirilmisC,KocaM,AhmedzadeM.Characterizationofanewlysynthesizedfluorescent benzofuranderivativeandusageasaselectivefiberopticsensorforfe(i)[j]. 犛犲狀狊. 犃犮狋狌犪狋狅狉狊犅 : 犆犺犲犿., 2007,122:450 456. [14] Esp sitobp,breuerw,cabantchikzi.designandapplicationsofmethodsforfluorescencedetectionofiron inbiologicalsystems[j]. 犅犻狅犮犺犲犿. 犛狅犮. 犜狉犪狀狊.,2002,30:729 732. [15] ValeurB,LerayI.Designprinciplesoffluorescentmolecularsensorsforcationrecognition[J]. 犆狅狅狉犱. 犆犺犲犿. 犚犲狏.,2000,205:3 40. [16] BazzicalupiC,BenciniA,BianchiA,FaggiE,GiorgiC,SantareliS,ValtancoliB.Coordinationpropertiesof polyamine macrocyclescontainingterpyridineunits[j]. 犆狅狅狉犱. 犆犺犲犿. 犚犲狏.,2008,doi:10.1016/j.ccr.2007. 07.024. GoodalW,WiliamsJAG.Anew,highlyfluorescentterpyridinewhichrespondstozincionswithalargered shiftinemission[j]. 犆犺犲犿. 犆狅犿犿狌狀.,2001,23:2514 2515. 犃犎犻犵犺犾狔犛犲狀狊犻狋犻狏犲犆狅犾狅狉犻犿犲狋狉犻犮犆犺犲犿狅狊犲狀狊狅狉犳狅狉犐狉狅狀 ( 犐犐 ) 犪狀犱犐狉狅狀 ( 犐犐犐 ) 犐狅狀狊 WANGJun 1,2,XU Quan qing 1,2,CHIShao ming 1,2,ZHANG Hui miao 1,2,FU Wen fu 1 (1. 犜犲犮犺狀犻犮犪犾犐狀狊狋犻狋狌狋犲狅犳犘犺狔狊犻犮狊犪狀犱犆犺犲犿犻狊狋狉狔, 犆犺犻狀犲狊犲犃犮犪犱犲犿狔狅犳犛犮犻犲狀犮犲狊, 犅犲犻犼犻狀犵 100190, 犘. 犚. 犆犺犻狀犪 ; 2. 犌狉犪犱狌犪狋犲犝狀犻狏犲狉狊犻狋狔狅犳犆犺犻狀犲狊犲犃犮犪犱犲犿狔狅犳犛犮犻犲狀犮犲狊, 犅犲犻犼犻狀犵 100049, 犘. 犚. 犆犺犻狀犪 ) 犃犫狊狋狉犪犮狋 :Inthisworkanewcompound(E) 4 (4 (2 (2 naphthalenyl)vinyl)phenyl) 2,2 :6, 2 terpyridine 犔 wassynthesized,characterizedandusedtorecognizeironions.uponaddition offe(i)orfe(i),thesolution( 犞 (CHCl 3 ) 犞 (ethanol)=1 20)of 犔 canshow magenta ororange redcolorinvisibleregion,respectively.andintheuv visspectrumof 犔 insolution thereemergetwocharacteristicpeaksat374and574nm.furthermore,theresponseof 犔 toi ronionsishighlysensitiveandselectiveeventhoughinthepresenceofothermetalions.the limitofdetection(lod)andlinearconcentrationrangeforiron(i)/iron(i)andiron(i+ I) werestudied,too. 犓犲狔狑狅狉犱狊 :colorimetry;chemosensor;terpyridinederivative;fe 2+ ;Fe 3+ Corespondingauthor:FU Wen fu,e mail:fuwf@mail.ipc.ac.cn