The synthesis of a new ligand (1) containing a single phenanthroline (phen) chromophore and a flexibly connected diethylenetriamine tetracarboxylic acid unit (DTTA) as a lanthanide (Ln) coordination site is reported [1 is 4-[(9-methyl-1,10-phenantrol-2-yl)methyl]-1,4,7-triazaheptane-1,1,7,7-tetraacetic acid]. From 1, an extended series of water-soluble Ln.1 complexes was obtained, where Ln is Eu(III), Tb(III), Gd(III), Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III). The stoichiometry for the association was found 1:1, with an association constant K(A) > or = 10(7) s(-1) as determined by employing luminescence spectroscopy. The luminescence and photophysical properties of the series of lanthanide complexes were investigated in both H2O and D2O solutions. High efficiencies for the sensitized emission, phi(se), in air-equilibrated water were observed for the Ln.1 complexes of Eu(III) and Tb(III) in the visible region (phi(se) = 0.24 and 0.15, respectively) and of Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III) in the vis and/or near-infrared region [phi(se) = 2.5 x 10(-3), 5 x 10(-4), 3 x 10(-5), 2 x 10(-5), 2 x 10(-4), 4 x 10(-5), and (in D2O) 4 x 10(-5), respectively]. For Eu.1 and Tb.1, luminescence data for water and deuterated water allowed us to estimate that no solvent molecules (q) are bound to the ion centers (q = 0). Luminescence quenching by oxygen was investigated in selected cases.

A two-component ligand system (1) containing 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) as the hosting unit for the lanthanide cations and an appended asymmetrically functionalized 1,10-phenanthroline (phen) as the chromophore was synthesized. The 1:1 complexes with Eu(3+), Gd(3+), Tb(3+), and Yb(3+) have been prepared and studied in aqueous solution. For Gd.1, a relaxivity value of 2.4 mM(-1) s(-1) has been measured at 20 MHz and 25 degrees C, which indicates that there are no water molecules in the first coordination sphere of the metal ion. The analysis of high resolution (1)H NMR spectra of Yb.1 supports this view and suggests the direct involvement of the phen moiety in the coordination of the metal ion. For Eu.1 and Tb.1, the absorption and luminescence spectra, the overall luminescence efficiencies, and the metal-centered (MC) lifetimes were obtained; coordination features were also determined by comparing luminescence properties in water and deuterated water. For Eu.1 and Tb.1, the overall emission sensitization (se) process in air-equilibrated water was found to be notably effective with phi(se) = 0.21 and 0.11, respectively. A detailed study of the steps originating from light absorption at the phen unit and leading to MC sensitized emission was performed.

We describe the syntheses, the 1H NMR studies in CD3OD and D2O as solvent, the X-ray characterization, and the luminescence properties in D2O solution of the two complexes Eu.1 and Er.1, where 1 is a dipartite ligand that includes (i) a 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) unit serving as hosting site for the metal center; and (ii) a phenanthroline unit which plays the role of light antenna for the sensitization process of the metal centered luminescence. In a previous report (Inorg. Chem. 2002, 41, 2777), we have shown that for Eu.1 there are no water molecules within the first coordination sphere. X-ray and 1H NMR results reported here are consistent with full saturation of the nine coordination sites within the Eu.1 and Er.1 complexes. In addition, these studies provide important details regarding the conformations, square antiprism (SAP) and twisted square antiprism (TSAP), adopted in solution by these complexes. The luminescence results are consistent with both an effective intersystem crossing (ISC) at the light absorbing phenanthroline unit (lambda(exc) = 278 nm) and an effective energy transfer (en) process from the phenanthroline donor to the cation acceptor (with unit or close to unit efficiency for both steps). In D2O solvent, the overall sensitization efficiency, phi(se), is 0.3 and 5 x 10(-6), for Eu.1 (main luminescence peaks at 585, 612, 699 nm) and Er.1 (luminescence peak at 1530 nm), respectively. The photophysical properties of both complexes are discussed with reference to their structural features as elucidated by the obtained 1H NMR and X-ray results.

Mixed self-assembled monolayers based on thiol-terpyridine and thiophenol molecules on gold surfaces show a tendency to form films whose composition is almost independent of the molar fraction of the components in the starting solution, and this indicates the formation of particularly stable assemblies.