Intramolecular electron (eT) and energy transfer (ET) have shown to occur in a covalently linked donor-acceptor (CLDA) system consisting of a naphthalene donor covalently linked through a polyamine chain connector to an anthracene acceptor; the connector has been chosen in order to switch ON or OFF the energy flux as a function of its protonation state as well as by co-ordination to Zn2+. The largest energy transfer efficiency (eta = 0.61) occurs for the fully protonated form (pH < 2), while at pH > 9 (eT) from the lone pairs of the nitrogens to the excited fluorophore takes place, leading to complete quenching of the emission. On the other hand at neutral and basic pH values. coordination of Zn2+ prevents the eT quenching allowing the ET process to occur. (C) 2002 Elsevier Science B.V. All rights reserved.

In this work a new water-soluble long-lifetime chemosensor, containing a polyamine unit connected to a complexed Ru(II) metal center, is described. Its crystal structure has been characterized by X-ray analysis. The polyamine macrocyclic unit is capable of anchoring cationic or anionic substrates, according to its protonation state. Examples of electron transfer involving the ruthenium complex core and the bound substrate are presented. The photocatalytic ability of such a system is illustrated by the oxidation of iodide to iodine promoted by light absorption at 436 nm.

The reaction of the cyanide anion [M(CO)(5)CN](-) (M = Cr or Mo) with metallocenes of Groups 4 and 6 produced polynuclear complexes of the type [CpCp 'M(CO){-NC-M ' (CO)(5)}]BF4 (M = M0, W; M ' = Mo, Cr, Cp '= Cp, Ind), Cp2TiCl{-NC-Mo(CO)(5)} and Cp2Ti{-NC-Mo(CO)(5)}(2). These complexes were characterised by H-1-, C-13- and Mo-95-NMR, IR and UV-vis spectroscopies, elemental analysis and examined by cyclic voltammetry. These methods show that the [M(CO)(5)CN]- ligands shift the electron density towards the metallocene centres. The complex [Cp2W(CO){-NC-Mo(CO)(5)}](+) is additionally examined by single crystal X-ray structure determination. The Density Functional Theory (DFT) calculations with the ADF program were performed on selected compounds to understand the nature of the redox processes taking place. Compared with a nitrile, the coordination of a [M(CO)-,CN]- fragment to the metallocene moiety does not significantly change the geometrical features. but leads to the stabilisation of the HOMO of the latter. with all the oxidation processes occurring in the pentacarbonyl moiety of the binuclear species. Time-dependent DFT calculations were used to identify the band appearing in the visible spectrum of Cp2TiCl{-NC-Mo(CO)(5)} as a Mo to Ti charge transfer. (C) 2001 Elsevier Science BN. All rights reserved.

The synthesis of the macrocyclic ligand 4,4 '-(2,5,8, 11,14-pentaaza[15])-2,2 ' -bipyridylophane (L3), which contains a pentaamine chain linking the 4,4 ' -positions of a 2,2 ' -dipyridine moiety, is reported. Protonation and Zn(II) complexation by L3 and by macrocycle L2, containing the same pentaamine chain connecting the 6,6 ' -positions of 2,2 ' -dipyridine, were studied by means of potentiometric, UV-vis, and fluorescent emission measurements. While in L2 all the nitrogen donor atoms are convergent inside the macrocyclic cavity, in L3 the heteroaromatic nitrogen atoms are located outside. Both ligands form mono- and dinuclear Zn(II) complexes in aqueous solution. In the mononuclear Zn(II) complexes with L2, the metal is coordinated inside the macrocyclic cavity, bound to the heteroaromatic nitrogen donors and three amine groups of the aliphatic chain. As shown by the crystal structure of the [ZnL2](2+) complex, the two benzylic nitrogens are not coordinated and facile protonation of the complex takes place at slightly acidic pH values. Considering the mononuclear [ZnL3](2+) complex, the metal is encapsulated inside the cavity, not coordinated by the dipyridine unit. Protonation of the complex occurs on the aliphatic polyamine chain and gives rise to translocation of the metal outside the cavity, bound to the, heteroaromatic nitrogens.

Reaction of Re-2{mu-O2CC(CH3)(3)}(4)Cl-2 with [(CO)(5)M-CN]Na (M = Cr, Mo, W) leads to tetranuclear complexes of formula Re-2{mu-O2CC(CH3)(3)}(4)[-NC-M(CO)(5)](2) (M = Cr, Mo, W). These complexes were characterized by H-1-, C-13-, and Mo-95-NMR, IR and Raman spectroscopy, elemental analysis and examined by cyclic voltammetry. The applied methods show the donor capabilities of the [(CO)(5)M-CN](-) ligands which shift electron density towards the Re centers weakening the Re-Re quadruple bond. The Re-Re bond lengths and the v(Re-Re) force constants are estimated based on the FT-IR and Raman examinations. Photochemical examinations and TG/MS experiments have also been conducted. The latter methods shows that the product complexes decompose around 100 degrees C, by first loosing their carbonyl substituents; as do the Cr, Mo, W precursor compounds. The dirhenium tetrapivalate unit decomposes only at higher temperatures in a distinct second step.

Reacting transition metal complexes in low oxidation states, containing one or two cyanide ligands, with methyltrioxorhenium(VII) leads to bridged mixed metal compounds in good yields. The Re(VII) core is then surrounded by five or six ligands, respectively. The strength of these CN bridges and thus the stability of the newly generated bimetallic compound strongly depends on the donor strength of the ligands surrounding of the Cr/Mo/W or Fe moiety. The stability of the mixed metal molecules is reflected in the temperature dependent behavior of their O-17-NMR spectra, in their IR (Re=O) stretching frequencies and force constants, as well as several other spectroscopic data. UV-vis absorption spectra show the appearance of charge transfer bands. In the case of the mixed Mo/Re complexes the Mo-95-NMR spectroscopy is also a helpful tool to examine the donor capability of the Mo moiety. The described compounds also show photosensitivity. (C) 1998 Elsevier Science S.A. All rights reserved.

The steady-state fluorescence emission spectra of the azacyclophanes 2,5,8,11-tetraaza[12] paracyclophane (L(1)), 2,6,9,13-tetraaza[14]paracyclophane (L(2)), 14,15,17,18-tetramethyl-2,5,8,11-tetraaza-[12]paracyclophane (L(3)) and 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane (L(4)) as a function of pH have been measured. The fully protonated species of each cyclophane gives the highest fluorescence-emission quantum yield. The shapes of the titration curves have been explained by the existence of an electron-transfer quenching effect from a non-protonated amine to the benzene chromophore. This effect is greater for macrocycles in which the first deprotonated amine group is closer to the benzene. The association constants for the interaction of the four fully protonated macrocycles with K-3[Co(CN)(6)] have been measured either by potentiometry or from fluorescence-emission measurements, and increase in the order L(3) approximate to L(4) < L(1) approximate to L(2). The photoaquation quantum yields of K-3[Co(CN)(6)] have been measured in the presence of the macrocycles L(1) and L(2). and indicate that three of the CN nitrogens of the complex are involved in adduct formation with the fully protonated macrocycles, as supported by molecular modelling.