Synthesis, Electrochemistry, and Photophysics of Aza-BODIPY Porphyrin Dyes
International audience; The synthesis of dyad and triad aza-BODIPY-porphyrin systems in two steps starting from an aryl-substituted aza-BODIPY chromophore is described. The properties of the resulting aza-BODIPY-porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination.
Soluble Heterometallic Coordination Polymers Based on a Bis-terpyridine-Functionalized Dioxocyclam Ligand
Soluble homo- and heterometallic coordination polymers containing transition metal cations (Cu(2+), Fe(2+), Co(2+), and Ni(2+) ions) were prepared in a two-step procedure using a polytopic bis(terpyridine)dioxocyclam ligand 1H(2) (dioxocyclam = 1,4,8,11-tetraazacyclotetradecane-5,7-dione). These supramolecular systems incorporate two different metal complexes, the metal cations being located both between two terpyridine units and in the macrocyclic framework. The characterization of these soluble architectures was investigated by cyclic voltammetry, mass spectrometry, viscosimetry, and UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies. Our results clearly indicate t…
Disease expression in women with hereditary angioedema
Udgivelsesdato: 2008-Jun-11 OBJECTIVE: Fluctuations in sex hormones can trigger angioedema attacks in women with hereditary angioedema. Combined oral contraceptive therapies, as well as pregnancy, can induce severe attacks. The course of angioedema may be very variable in different women. STUDY DESIGN: Within the PREHAEAT project launched by the European Union, data on 150 postpubertal women with hereditary angioedema were collected in 8 countries, using a patient-based questionnaire. RESULTS: Puberty worsened the disease for 62%. Combined oral contraceptives worsened the disease for 79%, whereas progestogen-only pills improved it for 64%. During pregnancies, 38% of women had more attacks, …
Synthesis and characterization of a 1,8-difunctionalized dissymmetrical cyclam copper(II) complex bearing pyridylmethyl and N,N-dimethylcarbamoylmethyl groups
The new dissymmetrical ligand 1-(N,N-dimethylcarbamoylmethyl)-8-(2-pyridylmethyl)-4,11-dimethyl-1,4,8,11-tetraazacyclotetradecane, 5, was synthesized and the physicochemical properties of its copper(II) complex, [CuII(5)](ClO4)2·CH3CN, were determined. UV–Vis, IR, ESR experiments, and X-ray analysis of [CuII(5)](ClO4)2·CH3CN were carried out. The X-ray structure of [CuII(5)](ClO4)2·CH3CN revealed a distorted square pyramid with the four coordinating nitrogen atoms of the macrocycle lying in the basal position. Curiously, the fifth ligand is the N,N-dimethylcarbamoylmethyl group through the oxygen atom and not the pyridylmethyl moiety.
First unequivocal synthesis of dissymmetrical trans N,N′-difunctionalized 1,4,8,11-tetraazacyclotetradecane
Abstract The first unequivocal synthesis of disymmetrical trans N,N′-difunctionalized tetraazamacrocycles in cyclam series is reported. This convenient four-step method can be used for the synthesis of various trans N,N′-difunctionalized tetraazamacrocycles bearing two different pendant donor arms.
Long-range electronic connection in picket-fence like ferrocene–porphyrin derivatives
The effects of a direct connection between ferrocene and porphyrin units have been thoroughly investigated by electrochemical and spectroscopic methods. These data not only reveal that substitution of the porphyrin macrocycle by one, two, three or four ferrocenyl groups strongly affects the electronic properties of the porphyrin and ferrocenyl moieties, they also clearly demonstrate that the metallocene centres are "connected" through the porphyrin-based electronic network. The dynamic properties of selected ferrocene-porphyrin conjugates have been investigated by VT NMR and metadynamic calculations. 1,3-Dithiolanyl protecting groups have been introduced on the upper rings of the ferrocene …