Synthesis, X-ray structure, photophysical properties, and theoretical studies of six-membered cyclometalated iridium(iii) complexes: revisiting Ir(pnbi)2(acac).

We have determined the X-ray structure of Ir(pnbi)2(acac) (pnbi = 2-phenanthren-9-yl-1-phenyl-1H-benzimidazole; acac = acetylacetonate), which exhibits a six-membered metallocycle around the Ir center. This result stands in sharp contrast to previously postulated structures of Ir(pnbi)2(acac), which assumed a five-membered metallocycle. In this paper, we focus on the relative stability of five- and six-membered Ir(C^N) ring structures. DFT calculations of the total energies of Ir-(C^N) complexes indicated that six-membered structures are more stable when bulky substituents are present in the benzimidazole unit. When the phenanthrene group of pnbi was replaced with a naphthalene moiety, DFT calculations predicted that five-membered cycles are more stable than six-membered rings, which was confirmed experimentally by a single-crystal X-ray diffraction analysis. The steric bulk of the phenanthrene-containing polyaromatic ring ligand thus induces greater interligand repulsion between the two ligands, which plays an important role in determining the cyclometalation route. The Ir complexes examined in this study exhibit red emission (λem ≈ 660 nm) with relatively low quantum yields.

Aggregation-Induced Fluorescence-to-Phosphorescence Switching of Molecular Gold Clusters.

Aggregation-induced optical responses are ubiquitous among a wide range of organic and inorganic compounds. Here, we demonstrate an unprecedented effect of aggregation on the photoluminescence (PL) profiles of [core + exo]-type [Au8]4+ clusters, which displayed a change in the dominant PL emission mode from fluorescence to phosphorescence-type upon aggregation. In solvents in which cluster molecules are highly soluble and exist as monomers, they displayed single PL bands at ∼600 nm at ambient temperatures. However, in solvents in which cluster molecules are less soluble and cluster aggregation is induced, a new PL band at ∼700 nm also emerged. Lifetime measurements revealed that the PL emissions at ∼600 and ∼700 nm had fluorescence and phosphorescence characters, respectively. Studies of the excitation spectra suggested that organized cluster assemblies were responsible for the lower-energy emission at ∼700 nm and had exceptionally high emission activity. Accordingly, intense phosphorescence-type emissions were observed in the solid state in which the quantum efficiencies were higher by two orders of magnitude than those of the corresponding monomeric forms in solution. This work provides an example of the critical effects of cluster aggregation events on their optical properties and shows the potential of such effects in the design of cluster-based materials with unique functions and properties.

Considerable Enhancement of Emission Yields of [Au(CN)2(-)] Oligomers in Aqueous Solutions by Coexisting Cations.

The photophysical properties of [Au(CN)2(-)] oligomers in aqueous solutions were investigated as functions of coexisting cations as well as the viscosity and temperature of solutions. A solution of [Au(CN)2(-)] in the concentration range of 0.03-0.2 mol/dm(3) exhibited emission peaks at 460-480 nm because of the presence of oligomers larger than trimers. Although the emission yields (ϕem) of K[Au(CN)2] solutions were <1%, it considerably increased to 43% when 1.0 mol/dm(3) tetraethylammonium chloride (Et4NCl) was added. The lifetimes of the main emission bands were also significantly varied with additional salts, e.g., KCl, 15 ns; Et4NCl, 520 ns. The time-resolved emission measurements of [Au(CN)2(-)] in a water/glycerol mixture indicated that the lifetimes were almost directly proportional to the inverse of the viscosity of the solution. On the other hand, the intrinsic lifetimes of dimers and trimers with weak emission in shorter wavelength regions were very short and independent of the viscosity of the solutions and coexisting cations (dimer, ∼25 ps; trimer, ∼2 ns). These results indicated that the deactivation of the excited-state [Au(CN)2(-)]n oligomers (n ≥ 4) was dominated by the dissociation of the oligomers to a shorter species (dimer or trimer). The hydrophobic interactions between tetraalkylammonium cations and CN ligands remarkably stabilized the larger oligomers and suppressed the dissociation of the excited-state oligomers, which enhanced the emission yield of the oligomers. This work provides a new method of "exciplex tuning" by changing the environment of excited-state [Au(CN)2(-)]n oligomers.

Coherent vibration and ultrafast dynamics upon bond formation in excited dimers of an Au(I) complex.

Au-Au bond strengthening in photoexcited dimers of an Au(I) complex is captured in solution as oscillations of femtosecond absorption signals. The subsequent dynamics, when compared to the trimer's data, confirm that the bent-to-linear structural change of the trimer occurs in the first few picoseconds.