0000000000224719
AUTHOR
José Manuel Lloris
Anion interaction with ferrocene-functionalised cyclic and open-chain polyaza and aza-oxa cycloalkanes
A family of ferrocene-functionalised receptors of different topologies have been used as receptors for anions. The compounds have been designed to contain both amine nitrogen and ether oxygen atoms and comprises from monoaza to pentaaza derivatives both open-chain (L1, L2, L3) or cyclic (L4, L5) and having from one to five ferrocenyl groups. Solution studies directed to determine the protonation constants of L1, L2 and L3 have been carried out in water (0.1 mol dm3 KNO3, 25 °C) and those of L4 and L5 in 1,4-dioxane-water (70:30 v/v, 0.1 mol dm -3 KNO 3, 25 °C). The protonation behaviour of the receptors can be explained taking into account electrostatic considerations. Speciation studies in…
Polyaza and azaoxa macrocyclic receptors functionalised with fluorescent subunits; Hg2+ selective signalling
A polyazacycloalkane containing naphthyl groups, 1,4,8,11-tetrakis(naphthylmethyl)-1,4,8,11-tetraazacyclotetradecane (L1), and the azaoxa cycloalkane receptors containing anthracenyl groups, 7,13-bis(anthracenylmethyl)-1,4,10-trioxa-7,13-diazacyclopentadecane (L2) and 10-anthracenylmethyl-1,4,7-trioxa-10-azacyclododecane (L3), have been synthesized and their activity as fluorescent chemosensors studied towards the metal cations Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+ in THF–water (70∶30 v/v, 0.1 mol dm−3 tetrabutylammonium perchlorate, 25 °C) for L1 and 1,4-dioxane–water (70∶30 v/v, 0.1 mol dm−3 potassium nitrate, 25 °C) for L2 and L3. The crystal structure of the complex [Cd(L1)(Cl)][PF6] has been…
Host molecules containing electroactive cavities obtained by the molecular assembly of redox-active ligands and metal ions
Self-assembly processes of nickel ions with the redox-active ligand 1,4,8,11-tetra(ferrocenylmethyl)-1,4,8,11-tetraazacyclotetradecane (Fc4cyclam) induces the formation of a redox-active cavity of potential use in electrocatalysis.
Cu2+-cyclam complex functionalised with naphthylmethyl fluorescent signalling subunits as fluorescent chemosensors for sulfate in aqueous environment.
Abstract The fluorescent behaviour of the polyazacycloalkane containing naphthyl groups 1,4,8,11-tetrakis(naphthylmethyl)-1,4,8,11-tetraazacyclotetradecane (L 1 ) and its Cu 2+ complex in the presence of anions are compared in aqueous environment (THF:water 70:30 v/v, 0.1 mol dm −3 tetrabutylammonium perchlorate, 25°C). The emission fluorescent intensity of the L 1 –Cu 2+ system is selectively enhanced in the presence of sulfate at acid pH.
Aza–oxa macrocyclic ligands functionalised with naphthylmethyl fluorescent groups
Abstract Compounds L 1 and L 2 were obtained by reaction of 2-(bromomethyl)naphthalene with 1,4,10-trioxa-7,13-diazacyclopentadecane and 1,4,7-trioxa-10-azacyclododecane, respectively. These receptors contain aza–oxa crowns attached covalently to fluorescent groups. The protonation and coordination behaviour of L 1 and L 2 against metal ions has been studied in dioxane:water (70:30 v/v, 25°C, 0.1 M potassium nitrate) using potentiometric methods. All metal ions studied form complexes with L 1 and L 2 with the logarithm of the formation constants L+M 2+ =[M(L)] 2+ in the sequence Cd 2+ ≅Pb 2+ , Zn 2+ 2+ for L 1 and Zn 2+ 2+ 2+ 2+ 2+ for L 2 . The fluorescent behaviour of L 1 and L 2 was stud…
A fluorescent chemosensor based on a ruthenium(II)-terpyridine core containing peripheral amino groups that selectively sense ATP in an aqueous environment
The selective sensing of the ATP anion in an aqueous environment over phosphate, sulfate, and chloride using a fluorescence chemosensor based on Ru(tpy)22+ cores attached to polyammonium groups is reported.
Co2+ Translocation in a Terpyridine−Cyclam Ditopic Receptor
The coordination behaviour of the ditopic receptor of 1-[p-(2,2′:6′,2′′-terpyrid-4′-yl)tolyl]-1,4,8,11-tetraazacyclotetradecane (L1) towards Co2+ in acetonitrile/water (70:30, v/v) has been investigated. At acidic pH values, the L1−H+−Co2+ system shows an oxidation wave at 150 mV vs. SCE, characteristic of Co2+ in a bis(terpyridine) environment. Upon addition of OH−, a reduction in the intensity of the wave at 150 mV is observed and a new oxidation wave appears at 1.30 V. This new wave is close to that found for [Co(cyclam)]2+ under similar working conditions. The electrochemical data thus suggest that there is a pH-controlled translocation of the Co2+ ion from the bis(terpyridine) to the c…
1,4,8,11-Tetrakis(4-ferrocenyl-3-azabutyl)-1,4,8,11-tetraazacyclotetradecane as a ferrocene-functionalised polyammonium receptor for electrochemical anion sensing
The interaction of the ferrocene-functionalised polyaza receptor 1,4,8,11-tetrakis(4-ferrocenyl-3-azabutyl)-1,4,8,11-tetraazacyclotetradecane (L1) with sulfate, phosphate and ATP has been studied potentiometrically in THF–water 70∶30 v/v (0.1 mol dm–3 tetrabutylammonium perchlorate, 25 °C). The molecular structure of the free receptor has been determined by single-crystal X-ray procedures. An electrochemical study on L1 as a function of the pH has been carried out in THF–water 70∶30 v/v in the presence of the sulfate, phosphate and ATP anions. The potential use of L1 as an anion sensing receptor is discussed in terms of the electrochemical and potentiometric data and its behaviour is compar…
Bis(terpyridyl)-ruthenium(II) units attached to polyazacycloalkanes as sensing fluorescent receptors for transition metal ions
A synthetic strategy has been devised for the preparation of new compounds in which terpyridyl fragments are linked to 1,4,8,11-tetraazacyclotetradecane (cyclam). Reaction of excess cyclam with 4′-[(4-bromomethyl)phenyl]-2,2′:2″,6′-terpyridine afforded the ligand 1-[4′-p-tolyl-(2,2′:6′,2″-terpyridyl)]-1,4,8,11-tetraazacyclotetradecane (L1) in which the tetraaza macrocycle was covalently attached to one benzyl-terpyridyl fragment. Under similar conditions reaction of cyclam with excess 4′-[(4-bromomethyl)phenyl]-2,2′:2″,6′-terpyridine gave the tetra substituted cyclam derivative 1,4,8,11-[4′-p-tolyl-(2,2′:6′,2″-terpyridyl)]-1,4,8,11-tetraazacyclotetradecane (L2). The multidentate ligand L2 w…
Transition metal binding properties of the redox-active 1,4,7,10,13,16-hexa(ferrocenylmethyl)-1,4,7,10,13,16-hexaazacyclooctadecane and its electrochemical behaviour in a non-aqueous solvent
Abstract Solution studies to elucidate the coordination behaviour and the electrochemical response of the ferrocene-functionalized polyazamacrocycle 1,4,7,10,13,16-hexa(ferrocenylmethyl)-1,4,7,10,13,16-hexaazacyclooctadecane (L1) by potentiometric methods and electrochemical techniques have been carried out. Potentiometric methods in the presence of Cd2+, Hg2+, Pb2+ and Zn2+ were carried out in 1,4-dioxane/water (70:30 v/v, 25°C, 0.1 mol dm−3 KNO3). Electrochemical studies were carried out in acetonitrile/dichloromethane (50:50 v/v, 25°C, 0.1 mol dm−3 TBAClO4) in the presence of transition metal ions and anions.