Ligand Exchange Triggered Photosensitizers – Bodipy‐Tagged NHC‐Metal Complexes for Conversion of ³O₂ to ¹O₂

A new imidazolium salt 3⋅HI with 8‐Bodipy as one N‐aryl substituent was synthesized from 8‐chloro‐Bodipy and imidazole followed by alkylation with iPrI. NHC‐metal complexes [CuCl(3)], [AuCl(3)], [Pd(allyl)Cl(3)] and [MCl(cod)(3)] and [MCl(CO)₂(3)] (M=Rh, Ir) were synthesized and the X‐ray crystal structure of [IrCl(CO)₂(3)] determined. The donation of NHC 3 was determined via IR (ν(CO) and cyclic voltammetry (Ir(I/II) redox potential). The photosensitizing properties of the complexes for the generation of ¹O₂ were quantified observing singlet oxygen quantum yield of up to Φs.o.=0.63. [IrCl(cod)(3)] displays poor Φs.o.=0.09, but, following a simple ligand exchange reaction of cod by two CO [IrCl(CO)₂(3)], a pronounced increase to Φs.o.=0.63 is observed

Facile Synthesis of Triptycene‐Azolium Salts and NHC‐Metal Complexes

The cycloaddition reactions of eleven substituted anthracenes with nosylated quinone imines provides a convenient route to the respective triptycenes. Following re‐aromatization, selective O‐butylation and cleavage of the nosyl‐group the respective triptycene anilines are obtained, which are converted into the respective imidazolium salts according to established procedures. Deprotonation of the imidazolium salts provide new triptycene‐NHC‐metal complexes (M=AuCl, RhCl(cod), IrCl(cod), RhCl(CO)₂, IrCl(CO)₂, PdI₂(py), PtCl₂(py), Pd(allyl)Cl) with unusual ligand sterics

Spontaneous emission of an atom in front of a mirror

Motivated by a recent experiment [J. Eschner {\it et al.}, Nature {\bf 413}, 495 (2001)], we now present a theoretical study on the fluorescence of an atom in front of a mirror. On the assumption that the presence of the distant mirror and a lens imposes boundary conditions on the electric field in a plane close to the atom, we derive the intensities of the emitted light as a function of an effective atom-mirror distance. The results obtained are in good agreement with the experimental findings.Comment: 8 pages, 6 figures, revised version, references adde