25 3 2009 3 CHINESE JOURNAL OF INORGANIC CHEMISTRY Vol.25 No.3 381~385 4-1 *,1 1 1,2 ( 1, 361005) ( 2, 361005) : -2,2 6,2 -,4 - -2,2 6,2 - (L), L (ZnL),, ZnL 1 1 2 1 2 1,ZnL : ; 4 - -2,2 6,2 - ; ; : O614.24 + 1; O611.5; O657.39 : A : 1001-4861(2009)00381-05 Complex of 4 -(p-dimethylaminobenzene)-2,2 :6,2 -terpyridine with Zinc Ion as a Fluorescent Compound Selective Recognition of Phosphate Ions HU Wang-Xia 1 LIN Li-Rong *,1 HUANG Rong-Bin 1 ZHENG Lan-Sun 1,2 ( 1 Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005) ( 2 State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, Fujian 361005) Abstract: The ligand L(L=4 -(p-dimethylaminobenzene)-2,2 6,2 -terpyridine) was synthesized and its complex with zinc ion was studied as anion binding receptor in polar solvent as V Ethanol V H2 O =9 1 mixture. The results indicated that the metal complex ZnL could act as efficient and selective sensor for phosphate ions. The UV-Vis and fluorescence 2- spectroscopic titration experiments indicated the formation of 1 2 complexes between ZnL and HPO 4 (or H 2 PO 4- ), and 1 1 complex between ZnL and PO 4. In addition, complex ZnL has a little response to F -, but there are no any responses to other anions such as Cl -, Br -, AcO - 2-, HSO 4-, SO 4 etc. The binding manner between the complex ZnL and phosphate ionswas proposed. Key words: Zn complex; 4 -(p-dimethylaminobenzene)-2,2 6,2 -terpyridine; anion recognition; phosphate ions [6~8],, [1~5] [9~11] [12,13], :2008-09-09 :2008-10-22 (No.K70025) (No.20571062) (No.2007CB815301) (No.20721001) * E-mail:linlr@xmu.edu.cn :,,25, ; :
382 25,,, 4.2 g 96% m.p.139~140 ( [21] :138~139 ), 1.4 4 -(4- )-2,2 6,2 - (L), [17], 2.5 mmol 1-(2- )-, 2.5 mmol 1-(2- )-(4- ) -1-2,2 6,2 (25.0 mmol),, 4.0 ml, 25 ml 6 h [14~18],,, [15] Goodall 2,2 6,2 -,,, 2,2 6,2-4, 47% m.p.:205~206. M + :352.4. - -2,2 6,2 - Found C, 78.13, H, 5.70, N, 15.92% ; Calc. for, C 23 H 20 N 4 : C, 78.38, H, 5.72, N, 15.90%. 1 H NMR(400, MHz,DMSO)δ/ppm:3.06 (s,6h,n (CH 3 ) 2 ),6.94 (d,2h,, J=2 Hz),7.46(t,2H,J=1.2 Hz),7.84(d,2H, J=9.2 Hz), 7.99(t,2H, J= 2.0 Hz), 8.72(m,4H),8.79(s, 2H) 1 1.1 2- (2-acetylpyri- dine,98%) Acros,, Bekeman DU-7400 -,Hitachi F-4500,Varian Unity 400MHz,Bruker Esquire 3000 plus,x-4 [19] 1.2 1-(2- )- 20 mmol 2-20 mmol 20 ml 1.5 ZnL 2 L 2.5 10-3 mol L -1 9 1 ZnL ( 1) 50 ml 5 h, 1 ZnL, Fig.1 Structure of ZnL complex 3.7 g, 57% m.p.199~200 ( :198~ 199 ) 2 1.3 1-(2- )-(4- ) -1-2.1 L Zn 2+ 2 L Zn 2+ 10 ml 15 ml L (1.5 mol L -1 ) 2.65 g 4-, Zn 2+ L 2a, 2-2.0, Zn 2+ L ml 24 h, L ( 509 nm),,, Zn 2+, Zn 2+,,, 509 nm L
3 :4-383 2 Fig.2 L 438 nm, 372 322 310 nm 3, L Zn 2+ ; Zn 2+,438 nm, Zn 2+ 1 1, Zn 2+ 418 nm, 424 nm, 1 1 ( 3b) L Zn 2+ 2 1 L Zn 2+ 1 1, ; (c [22] L Zn 2+ L =2.5 10-5 mol L -1 )(a) L Zn 2+ 1 1 2.27 10 8 L mol -1, L L Zn 2+ Fluorescence spectra of the ligand L varied with different concentration of Zn 2+ (a) and the fluorescence intensity at the maxium wavelength varied with the ratio of c 2+ Zn to c L 2.2 ZnL L ; L Zn 2+ 1 1, L Zn 2+,L 475 nm 1 2 1 1 ZnL ( 2b ), L, Zn 2+ 2-4a, PO 4 HPO 4 H 2 PO 4- ZnL,L Zn 2+ 2 1,,F - ZnL L Zn 2+ 1 1,L Zn 2+, Cl -, 1 1 NO,AcO - - ZnL,HSO 4 L Zn 2+ 2-3a, SO 4 ZnL L 2, ZnL 290 nm 350 nm; Zn 2+, 10% L, Zn 2+, ZnL F - ( 4b), ZnL 3 Fig.3 L Zn 2+ (c L =2.5 10-5 mol L -1 )(a) 438 nm Zn 2+ L a in pure ethanol solvent; b in 90% ethanol solution, c ZnL =2.5 10-5 mol L -1, c PO4 =8.20 10-5 mol L -1, c F -=c Cl -=c NO3 -=c AcO -=c HSO4 -=c 2- SO4 Absorption spectra of the ligand L varied with =5.00 10-4 mol L -1 different concentration of Zn 2+ (a) and the 4 ZnL absorption intensity at 438 nm varied with Fig.4 Fluorescence spectra of ZnL in the presence the ratio of c 2+ Zn to c L of different kinds of anion
384 25 2.3 mol -1, 1.8 10 8 ZnL H 2 PO 4- ZnL ( 5), ZnL, H 2 PO 4- ZnL 2 1, H 2 PO 4- Zn 2+ L, H 2 PO 4-, H 2 PO 4- ZnL 6a 10%, 2, ZnL H 2 PO 4- ;,ZnL H 2 PO 4-, H 2 PO 4-2 ( 5b ), 418 nm ( 0.99), H 2 PO 4- ZnL 2, H 2 PO 4- ZnL 2 1 447 nm, [23], H 2 PO 4- H 2 PO 4- ZnL 1.8 10 4 L ZnL 2 1 ( 6b) ZnL H 2 PO 4-, H 2 PO 4- ZnL ;, H 2 PO 4-2- ZnL HPO 4 ZnL H 2 PO 4-, H 2 PO 4- PO 4 ZnL ( 5a), PO 4 ( 0.99, 5a ), PO 4 ZnL 1 1 [23] PO 4- ZnL 2.2 10 5 L mol -1 PO 4 ZnL PO 4 ZnL 1 1, PO 4 PO 4 seen in a and H 2PO 4- in b, inset is the reciprocal variation of fluorescence intensity value at the maxium wavelength varied with the reciprocal concentration of phosphate ion, c ZnL =2.5 10-5 mol L -1 6 ZnL H 2 PO 4- (a) ZnL 418 nm 5 ZnL H 2 PO 4- Fig.6 Absorption spectra of ZnL varied with different Fig.5 Fluorescence spectra of ZnL varied with different concentration of phosphate ion concentration of PO 4 (a) and the absorption value at 418nm varied with the ratio of c PO4 to c Zn 2+
3 :4-385 Zn 2+ L 7a 10%,ZnL PO 4,,ZnL PO 4, 418 nm, PO 4 ZnL : 426 nm,, [1] Schneider H, Vogelhuber K M, Schinle F, et al. J. Am. Chem. PO 4 ZnL 1 1 ( 7b) Soc., 2007,129:13022~13026 [2] Chen C L, Lin T P, Chen Y S, et al. Eur. J. Org. Chem., 2007, ZnL,H 2 PO 4-70:3999~4010 2- HPO 4 ZnL 2 1 PO 4 ZnL 1 [3] Santos M G, Fern 觃 ndez P B, Plush S E, et al. Chem. Commun., 1, 2007,3389~3391, [4] Kondo S I, Fukuda A, Yamamura T, et al. Tetrahedron Letters.,, 2007,48:7946~7949 Zn 2+ [5] Quinlan E, Matthews S E, Gunnlaugsson T. J. Org. Chem.,,ZnL 2007,72:7497~7503,ZnL [6] Fillaut J L, Andriès J, Perruchon J, et al. Inorg. Chem., 2007, 46(15):5922~5932 [7] Lin T P, Chen C Y, Wen Y S, et al. Inorg. Chem., 2007,46 (22):9201~9212 [8] Brombosz S M, Zucchero A J, Phillips R L, et al. Org.Lett., 2007,9(22):4519~4522 [9] Sato K, Sadamitsu Y C, Araib S, et al. Tetrahedron Letters., 2007,48:1493~1496 [10]Lee D H, Im J H, Son S U, et al. J. Am. Chem. Soc., 2003, 125:7752~7753 [11]Lee D H, Kim S Y, Hong J I. Angew. Chem. Int. Ed., 2004, 43:4777~4780 [12]ZHOU Li-Li ( ), WU Jia-Sheng ( ), ZHANG Xiao-Hong( ), et al. Chinese J. Chem.(Huaxue Xuebao), 7 ZnL PO 4 2004,62(19):1862~1866 (a) ZnL 418 nm PO 4 [13]Shang X F, Lin H, Cai Z S, et al. Talanta, 2007,73:296~303 ZnL Fig.7 Absorption spectra of ZnL varied with different [14]Lainé P, Bedioui F, Ochsenbein P, et al. J. Am. Chem. Soc., concentration of PO 2002,124(7):1364~1377 4 (a) and the absorption value at 418 nm varied with the ratio of c [15]Goodall W, Williams J A. Chem. Commun., 2001,2514~2515 PO4 to c Zn 2+ [16]Tessore F, Roberto D, Ugo R, et al. Inorg. Chem., 2005,44 F - ZnL (24):8967~8978, F - [17]Mutai T, Cheon J D, Arita S. J. Chem. Soc., Perkin Trans. ZnL 1 1, 2001,2:1045~1050 [18]Brombosz S M, Zucchero A J, Phillips R L. Org. Lett., 2007, 2.46 10 3 L mol -1 ; 9(22):4519~4522 418 nm F - [19]Hanabusa K, Hirata T, Inoue D, et al. Physicochemical and, F - ZnL Cl - Engineering Aspects, 2000,169:307~315 [20]Wang J X, Pappalardo M, Keene F R. Aust. J. Chem., 1995, 48:1425~1436 3 [21]Masaki M, Oji A, Hiramatsu K, et al. J. Chem. Soc. Perkin Trans.2, 1992,2:201~206 4 - -2,2 6,2 - [22]Valeur B, Pouget J, Bourson J, et al. J. Phys. Chem., 1992,, 1 1 96:6545~6549, Zn 髤 [23]Catena G C, Bright F V. Anal. Chem., 1989,61:905~909