Preparation and Photophysical Properties of (tridentate) Iridium(III) Emitters: Pincer Coordination of 2,6-Di(2-pyridyl)phenyl.

The way to prepare molecular emitters [5t + 4t'] of iridium(III) with a 5t ligand derived from the abstraction of the hydrogen atom at position 2 of the aryl group of 1,3-di(2-pyridyl)benzene (dpybH) is shown. In addition, the photophysical properties of the new emitters are compared with those of their counterparts resulting from the deprotonation of 1,3-di(2-pyridyl)-4,6-dimethylbenzene (dpyMebH), at the same position, which are also synthesized. Treatment of 0.

η -Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes.

Molecular phosphorescent heteroleptic bis-tridentate iridium(III) emitters have been prepared via η -arene intermediates. In the presence of 4.0 mol of AgOTf, the complex [(IrCl{κ -N,C,N-(pyC HMe py)})(μ-Cl)] (1; pyC H Me py=1,3-di(2-pyridyl)-4,6-dimethylbenzene) reacted with 9-(6-phenylpyridin-2-yl)-9H-carbazole (PhpyCzH) and 2-phenoxy-6-phenylpyridine (PhpyOPh) to give [Ir{κ -N,C,N-(pyC HMe py)}{κ -C,N,C'-(C H pyCzH)}]OTf (2) and [Ir{κ -N,C,N-(pyC HMe py)}{κ -C,N,C'-(C H pyOPh)}]OTf (3).

Synthesis and dynamic behaviour of zwitterionic [M(η(6)-C6H5-BPh3)(coe)2] (M = Rh, Ir) cyclooctene complexes.

The synthesis and structural characterization of zwitterionic [(η(6)-C6H5-BPh3)M(coe)2] (M = Rh, Ir) cyclooctene complexes is described. Both complexes exhibit an unusual exo-endo conformation of both cyclooctene ligands in the solid state. However, an equilibrium between the endo-endo and exo-endo rotational isomers arising from the hindered rotation about the metal-cyclooctene bond is observed in solution.

Dinuclear pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture.

A series of dinuclear pyridine-4-thiolate (4-Spy)-bridged rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 [diolef = 1,5-cyclooctadiene (cod), M = Rh (1), Ir (2); diolef = 2,5-norbornadiene (nbd), M = Rh (3)] were prepared by the reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) was obtained by the reaction of [Rh(acac)(CO)(PPh3)] (acac = acetylacetonate) with 4-pySH. Compounds 1-4 were assessed as metalloligands in self-assembly reactions with the cis-blocked acceptors [M(cod)(NCCH3)2](BF4) [M = Rh (a), Ir (b)] and [M(H2O)2(dppp)](OTf)2 [M = Pd (c), Pt (d); dppp = 1,3-bis(diphenylphosphino)propane].

Bis(hydrosulfido)-bridged dinuclear rhodium(I) complexes as a platform for the synthesis of trinuclear sulfido aggregates with the core [MRh2(μ3-S2)] (M = Rh, Ir, Pd, Pt, Ru).

The reaction of [Rh(μ-SH)(CO)(PPh(3))](2) or [Rh(μ-SH){P(OPh)(3)}(2)](2) with [Cp*MCl(2)](2) (M = Rh, Ir) in the presence of NEt(3) afforded the Rh(3) and IrRh(2) sulfido-bridged compounds [Cp*M(μ(3)-S)(2)Rh(2)(CO)(2)(PPh(3))(2)] (M = Rh, 1; Ir, 2) and [Cp*Rh(μ(3)-S)(2)Rh(2){P(OPh)(3)}(4)] (3). The reaction with [MCl(2)(cod)] (M = Pd, Pt), cis-[PtCl(2)(PPh(3))(2)] or [(η(6)-C(6)H(6))RuCl(2)](2) under the same experimental conditions gave [(cod)M(μ(3)-S)(2)Rh(2){P(OPh)(3)}(4)] (M = Pd, 6; Pt, 7), [(cod)M(μ(3)-S)(2)Rh(2)(CO)(2)(PPh(3))(2)] (M = Pd, 8; Pt, 9), [(PPh(3))(2)Pt(μ(3)-S)(2)Rh(2)(CO)(2)(PPh(3))(2)] (10) and [(η(6)-C(6)H(6))Ru(μ(3)-S)(2)Rh(2)(CO)(2)(PPh(3))(2)] (12), with PdRh(2), PtRh(2) and RuRh(2) trimetallic cores. The aggregates derived from [Rh(μ-SH)(CO)(PPh(3))](2) were isolated as a mixture of trans and cis isomers in which the trans isomer predominates.