propanone singlet excited state was detected on the reaction path to the metallaketene species. This metallacyclopropanone excited state species has a lifetime of less than 100 ps and a characteristic bridging carbonyl band at 1770 cm −1 . The tungsten ketene species was also detected but in contrast to the chromium system, this forms directly from a low-lying triplet excited state. The electrochemical release of CO showed a greater efficiency for the chromium complex when compared to the tungsten.

The efficient on/off switching of fluorescence from thienyl- and phenyl-substituted porphyrin-ferrocene dyads is achieved through redox control of excited-state electron-transfer quenching.

a b s t r a c t A highly selective dopamine sensor was fabricated by doping polypyrrole with a sulfonated ␤-cyclodextrin. This composite material enabled the selective sensing of dopamine in the presence of a large excess of ascorbic acid and prevented the regeneration of dopamine through the homogeneous catalytic reaction of the ascorbate anion with the dopamine-o-quinone. A single redox wave, corresponding to the oxidation of dopamine, was observed in dopamine/ascorbate mixtures, giving a truly selective dopamine sensor. The limit of detection was measured as 3.2 × 10 −6 M for dopamine.

The influence of the thiophene ring on the ground and excited state properties of the porphyrin ring is investigated, when substituted at the meso-position. A series of mono-, di-, tri-, and tetra- meso-thien-2-yl porphyrins are studied and discussed with respect to the reference compounds zinc(II)-5,10,15,20-tetra(thien-2'-yl)porphyrin ( 1a) and zinc(II)-5,10,15,20-tetraphenylporphyrin (ZnTPP). The extended conjugated system zinc(II)-5-(5'-(5''-ethynyl-2''-thiophenecarboxaldehyde)thien-2'-yl)-10,15,20-triphenylporphyrin ( 4d) is also studied and shows enhanced charge transfer character due to the presence of the terminal aldehyde accepting group. A detailed analysis of ground and excited state UV-vis absorption, steady-state and time-resolved fluorescence, laser flash photolysis, and electrochemical data all point toward substantial electronic communication between the central Zn(II) porphyrin ring and the meso-thien-2-yl substituents, which is evident from excited state charge transfer character.