The luminescence properties of Re(I) complexes incorporating the dcbpy ligand (dcbpy = n,n′-dicarboxylic acid-2,2′-bipyridine; n = 3, 4) were investigated as well as their utility as Pb2+ sensors. An unusual binuclear complex of the 3,3′- species was isolated. The emission intensity and lifetime for all complexes were found to be highly temperature-dependent, with quantum yields and lifetimes dramatically greater at 77 K than at room temperature. The monomeric 3,3′-dcbpy Re(I) complex demonstrates nearly 1:1 binding with Pb2+. The effect of this lead binding on the emission intensity is great, but the low quantum yields allow only for detection of the metal at the micromolar level. The binding of Pb2+ to the 4,4′-dcbpy complex is modeled and the interaction is demonstrated to involve two binding sites.
Rhenium Luminescence Lead detection Bipyridine dicarboxylic acid
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The authors are grateful to Dr. Cynthia Day, Department of Chemistry, Wake Forest University, for the X-ray data collection. The cif file of the structure is available from the authors. We gratefully acknowledge support by NSF CHE 04-10061.
Demas JN, DeGraff BA (1991) Design and applications of highly luminescent transition metal complexes. Anal Chem 63(17):830A–836ACrossRefGoogle Scholar
Anzenbacher P Jr, Tyson DS, Jursikova K, Castellano FN (2002) Luminescence lifetime-based sensor for cyanide and related anions. J Am Chem Soc 124(22):6232–6233PubMedCrossRefGoogle Scholar
Jain A, Xu W, Demas JN, DeGraff BA (1998) Binding of luminescent ruthenium(II) molecular probes to vesicles. Inorg Chem 37(8):1876–1879CrossRefGoogle Scholar
Hagerman ME, Salamone SJ, Herbst RW, Payeur AL (2002) Tris(2,2′-bipyridine)ruthenium(II) cations as photoprobes of clay tactoid architecture within hectorite and laponite films. Chem Mater 15(2):443–450CrossRefGoogle Scholar
Perkovic MW (2000) Allosteric manipulation of photoexcited state relaxation in (bpy)2RuII(binicotinic acid). Inorg Chem 39(21):4962–4968PubMedCrossRefGoogle Scholar
Sacksteder L, Zipp AP, Brown EA, Streich J, Demas JN, DeGraff BA (1990) Luminescence studies of pyridine a-diimine rhenium(I) tricarbonyl complexes. Inorg Chem 29(21):4335–4340CrossRefGoogle Scholar
Hung C-Y, Wang T-L, Jang Y, Kim WY, Schmehl RH, Thummel RP (1996) Dipyrido[4,3-b;5,6-b]acridine derivatives and their ruthenium(II) complexes. Inorg Chem 35(20):5953–5956CrossRefGoogle Scholar
Zipp AP, Sacksteder L, Streich J, Cook A, Demas JN, DeGraff BA (1993) Luminescence of rhenium(I) complexes with highly sterically hindered a-diimine ligands. Inorg Chem 32(24):5629–5632CrossRefGoogle Scholar
Liu Q, Mudadu MS, Schmider H, Thummel R, Tao Y, Wang S (2002) Tuning the luminescence and electroluminescence of diphenylboron complexes of 5-substituted 2-(2′-Pyridyl)indoles. Organometallics 21(22):4743–4749CrossRefGoogle Scholar
Higgins B, DeGraff BA, Demas JN (2005) Luminescent transition metal complexes as sensors: structural effects on pH response. Inorg Chem 44(19):6662–6669PubMedCrossRefGoogle Scholar
Dholakia S, Gillard RD, Wimmer FL (1985) 3,3′-Dicarbomethoxy-2,2′-bipyridyl complexes of palladium(II), platinum(II) and rhodium(III). Polyhedron 4(5):791–795CrossRefGoogle Scholar
Sheldrick GM (1996) SADABS: program for empirical absorption of area detector data. University of Gottingen, Gottingen, GermanyGoogle Scholar
Sheldrick GM (1997) SHELXTL Version 5.1 reference manual. Bruker AXS, Madison, WIGoogle Scholar
Wu F, Riesgo E, Pavalova A, Kipp RA, Schmehl RH, Thummel RP (1999) Ruthenium(II) complexes of 2-Aryl-1,10-phenanthrolines: synthesis, structure, and photophysical properties. Inorg Chem 38(24):5620–5628PubMedCrossRefGoogle Scholar
McFarland SA, Magde D, Finney NS (2005) Conformational control of excited-state dynamics in highly distorted Ru(II) polypyridyl complexes. Inorg Chem 44(11):4066–4076PubMedCrossRefGoogle Scholar
Lai RY, Chiba M, Kitamura N, Bard AJ (2001) Electrogenerated chemiluminescence. 68. Detection of sodium ion with a ruthenium(II) complex with crown ether moiety at the 3,3′-positions on the 2,2′-bipyridine ligand. Anal Chem 74(3):551–553CrossRefGoogle Scholar