An entirely earth‐abundant chromophore‐relay water oxidation catalyst triad system, which is robust and efficient at neutral pH, is presented. The synthesis involves the coordination of a porphyrin derivative to a bridging Fe(CN)5 group, which is then reacted with Co ions to prepare a covalently linked chromophore–Prussian blue analogue assembly. Light‐driven water oxidation studies in the presence of an electron scavenger indicate that the triad is active and it maintains a steady activity for at least three hours. Transient absorption experiments and computational studies reveal that the Fe(CN)5 group is more than a linker as it takes part in electron‐transfer and co‐operates with porphyrin in the charge separation process.
We describe the characterization of a new optical CO(2) sensor based on the change in the fluorescence signal intensity of 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) in green chemistry reagents--room-temperature ionic liquids (RTILs). As far as we are aware, this is the first time RTILs, 1-methyl-3-butylimidazolium tetrafluoroborate (RTIL-I) and 1-methyl-3-butylimidazolium bromide (RTIL-II), have been used as matrix materials with HPTS in an optical CO(2) sensor. It should be noted that the solubility of CO(2) in water-miscible ionic liquids is approximately 10 to 20 times that in conventional solvents, polymer matrices, or water. The response of the sensor to gaseous and dissolved CO(2) has been evaluated. The luminescence intensity of HPTS at 519 and 521 nm decreased with the increasing concentrations of CO(2) by 90 and 75% in RTIL-I and RTIL-II, respectively. The response times of the sensing reagents were in the range 1-2 min for switching from nitrogen to CO(2), and 7-10 min for switching from CO(2) to nitrogen. The signal changes were fully reversible and no significant hysteresis was observed during the measurements. The stability of HPTS in RTILs was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 7 months. Our stability tests are still in progress.
A Zn phthalocyanine-resorcinarene cavitand hybrid was prepared. The axial binding and host-guest interactions of this hybrid with a pyridinyl-pyrene were investigated by UV-vis and fluorescence spectroscopic means, revealing the encapsulation of the guest maintained by axial coordination to the Zn phthalocyanine. Energy transfer between the pyrene and the phthalocyanine was evidenced.
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