在本論文中，我們合成了兩種具有偵測重金屬能力的銥(III)金屬錯合物：[Ir(pba)2(pbi)]以及[Ir(pba)2(pbi)]。位在配位基pbi上之氮原子所具有的孤電子對讓我們得以具有偵測Hg2+、Ce3+、Cr3+以及Fe3+等金屬離子的能力。氮原子與這些金屬陽離子之間的作用力表現在吸收光譜與放光光譜的變化中。從吸收光譜中我們可以看到等吸收點的存在，而從放光光譜中我們也發現了與金屬離子結合前後，錯合物的放光強度也有不同程度的改變。我們使用了B3LYP的理論方法，並配合基底函數6-31G*後，得以從密度泛函理論中找到解釋這些光物理現象變化的方法。此論文也是本實驗室第一篇藉由理論計算結果而成功預測吸收光譜位移現象的論文。 為了確認錯合物中醛基以及氫氧基的部位確實沒有與金屬陽離子結合的能力，我們也合成出[Ir(pba)2(bpy)][Cl]以及[Ir(ppm)2(bpy)][Cl]以作為對照。即使[Ir(pba)2(bpy)][Cl]的放光強度比[Ir(pba)2(pbi)]還要強很多，但是[Ir(pba)2(bpy)][Cl]依然沒有表現出能夠偵測任何金屬的能力。值得注意的是，[Ir(ppm)2(bpy)][Cl]這個經過還原後的衍生物表現出可以稍微偵測到Ag+、Ca2+、Ni2+以及Zn2+的能力。同時我們也發現到此錯合物對於水有著極佳的溶解度。

Two Ir(III)-complexes, [Ir(pba)2(pbi)] and [Ir(ppm)2(pbi)] {pba = 4-(pyridin-2-yl)benzaldehyde,pbi=2-(pyridin-2-yl)-1H-benzo[d]imidazole , ppm=(4-(pyridin-2-yl)phenyl)methanol }, capable of sensing heavy metal ions have been synthesized in this study. The lone-paired electrons on the nitrogen atom of the pbi ligand is responsible for detecting the following metal ions: Hg2+, Ce3+,Cr3+ and Fe3+. The N(pbi)—metal Ion interactions result in variations of both UV-Vis spectra (by a blue-shift of about 7 nm) and luminescence spectra (by the change of luminescence intensities). These changes of photophysical data have found to be well predicted by the density functional theory calculations using B3LYP correlation-exchange functional formalism and 6-31G* basis set. More interestingly, the calculated results have been FIRST employed at this lab to successfully predict the directions of the shift (red or blue) in a UV-Vis absorbance-wavelength profile. In order to examine the failure of the carbonyl (in pba) or the hydroxyl oxygen atoms in semi-coordination with metal ions, we have also prepared [Ir(pba)2(bpy)][Cl], in which the carbonyl oxygen loses the ability to detect metal ions at all although the luminescence intensities were much higher than [Ir(pba)2(pbi)]. It is noteworthy that the reduced analogue,[ Ir(ppm)2(bpy)][Cl], has revealed a slight ability to detect some metal ions including Ag+, Ca2+, Ni2+ and Zn2+. Nonetheless, this poor sensor nature of [Ir(ppm) 2(bpy)][Cl] could be, more or less, counterbalanced by its high solubility in water.

1. Hassan A. A. ; Joachim P. K. ;Michael J. S.；Sensors 2006, 6, 435.
2. Huarui H. ; Kenneth J. ; Chao L.；Analytica Chimica Acta，611, 2, 2008,197.
3. Fages F. ; Desvergne J.P. ; Bouas-Laurent H. ; Marsau P. ; Lehn J-P. ; Kotzyba-Hilbert F.
; Albrecht-Gary A.M. ; J Am Chem Soc 111:8672
4. Hong B. ; Kai J. ; Ren Y. ; Han J. ; Zou Z. ; Ahn CH. ; Kang KA；Adv Exp Med Biol. 2008;614:265.
5. de Silva, A. P.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Huxley, A. J. M.; McCoy, C. P.; Rademacher, J.T.
; Rice, T. E.?Chem.Rev.1997,97,1515.
6. Valeur B. ; Leray I.?Coord.Chem.Rev.2000,205,3.
7. de Silva A. P. ; de Silva S. A. ; J. Chem. Soc., Chem. Commun., 1986, 1709
8. Konopelski J.P. ; Kotzyba-Hilbert F. ; Lehn J.M. ; Desvergne J.P. ; Fages F. ; Castellan A.
; Bouas-Laurent H. ; J Chem Soc Chem Commun 7:433
9. Fages F. ; Desvergne J.P. ; Bouas-Laurent H. ; Marsau P. ; Lehn J.P. ; Kotzyba-Hilbert F.
; Albrecht-Gary A.M. ;. ; J Am Chem Soc 111:8672
10. Akkaya E.U; Huston M.E. ; Czarnik A.W. ;. J Am Chem Soc 112:3590
11. Sclafani J.A. ; Maranto M.T. ; Sisk T.M. ; Tetrahedron Lett 13:2193
12. Fabbrizzi L.; Licchelli M. ; Pallavicini P. ; Inorg Chem 35:1733
13. Nanjappan P. ; J Am Chem Soc 109:1826
14. Huston, M. E.; Haider, K.W. ; J Am Chem Soc 110:4460
15. Fabbrizzi L. ; Licchelli M. ; Pallavicini P. ; Perotti A. ;Angew Chem Int Ed Engl 33:1975
16. Kramer R. ; Angew Chem Int Ed Engl 37:772
17. Fabbrizzi L. ; Lichelli M. ; Pallavicini P. ; Perotti A. ; Taglietti A,Sacchi D. ; Chem Eur J 2:167
18. Sung K.S. ; Fu H.K. ; Hong S.H.；J Fluoresc 2007 17:383–389.
19. Huang W.S. ; Lin J.T. ; Chien C.H.. ; Tao Y.T. ; Sun S.S. ;Wen Y.S.；Chem. Mater. 2004, 16, 2480-2488
20. Kenneth K.W. ; Chung C.K. ; Zhu N.Y.；Chem. Eur. J. 2003, 9, No. 2,475-483.
21. (a) Nugent, W. A.; Harlow, R. L. J. Am. Chem. Soc. 1994, 116, 6142-6148;
(b)Roothan, C. C. J. Rev. Mod. Phys. 1951, 23, 69-89.
22. Weeny, R. M.; Dierksen, G.; Nugent, W. A.; Harlow, R. L. J. Chem. Phys. 1968,49, 4852-4856.
23. Slater, J. C. Quantum Theory of Molecular and Solids. Vol. 4:
The Self-Consistent Field for Molecular and Solids (McGraw-Hill, New York, 1974).
24. (a) Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864-B871;
(b) Kohn, W.;Sham, L. J. Phys. Rev. 1965, 140, A1133-A1138;
(c) Salahub, D. R.; Zerner, M.C. Eds. The Challenge of d and f Electrons (ACS, Washington, D.C., 1989);
(d)Parr, R. G.; Yang, W.Density-functional theory of atoms and molecules (OxfordUniv. Press, Oxford, 1989).
25. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652;
(b) Becke, A. D. Phys.Rev. 1988, A38, 3098-3100.
26. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, 785-789.
27. (a) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989, 157,200-206;
(b) Wong, N. B.; Cheung, Y. S.; Wu, D. Y.; Ren, Y.; Wang, X.; Tian,A. M.; Li, W. A. J. Mol. Struct.
(Theochem) 2000, 507, 153-156;
(c) Aubauer, C.;Klapotke, T. M.; Schulz, A. J. Mol. Strust. (Theochem) 2001, 543, 285-297;
(d)Yang, W.; Drueckhammer, D. G. J. Am. Chem. Soc. 2001, 123, 11004-11009;
(e)Anane, H.; Boutalib, A.; Nebot-Gil I.; Tomas, F. J. Phys. Chem. A 1998, 102,7070-7073;
(f) Reed, A. E.; Weinhold, F. J. Chem. Phys. 1986, 84, 5687-5705;
(g) Weinhold, F. J. Mol. Struct.(Theochem) 1997, 398, 181-197;
(h) Mitzel, N.W.; Losehand, U. J. Am. Chem. Soc. 1998, 120, 7320-7327;
(i) Hobza, P.;Sponer, J.; Cubero, E.; Orozco, M.; Luque, F. J. J. Phys. Chem. B 2000, 104,6286-6292;
(j) Ananthavel, S. P.; Manoharan, M. Chem. Phys. 2001, 269, 49-57;
(k) Wilkens, S. J.; Weatler, W. M.; Weinhold, F.; Markley; J. L. J. Am. Chem. Soc. 2002, 124, 1190-1191.
28. National Chung Cheng University , Biing-Chiau Tzeng, Associate Professo , Inorganic Chemistry,
Material Chemistry Lab unpublished data.