Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence

The synthesis, electrochemistry, and photophysics of a series of square planar Pt(II) complexes are reported. The complexes have the general structure C∧NPt(O∧O),where C∧N is a monoanionic cyclometalating ligand (e.g., 2-phenylpyridyl, 2-(2‘-thienyl)pyridyl, 2-(4,6-difluorophenyl)pyridyl, etc.) and O∧O is a β-diketonato ligand. Reaction of K2PtCl4 with a HC∧N ligand precursor forms the chloride-bridged dimer, C∧NPt(μ-Cl)2PtC∧N, which is cleaved with β-diketones such as acetyl acetone (acacH) and dipivaloylmethane (dpmH) to give the corresponding monomeric C∧NPt(O∧O) complex. The thpyPt(dpm) (thpy = 2-(2‘-thienyl)pyridyl) complex has been characterized using X-ray crystallography. The bond lengths and angles for this complex are similar to those of related cyclometalated Pt complexes. There are two independent molecular dimers in the asymmetric unit, with intermolecular spacings of 3.45 and 3.56 A, consistent with moderate π−π interactions and no evident Pt−Pt interactions. Most of the C∧NPt(O∧O) complexes...

Synthesis and characterization of phosphorescent cyclometalated platinum complexes.

One goal of this critical review is to provide advanced methodologies for systematic preparation of transition-metal based phosphors that show latent applications in the field of organic light emitting diodes (OLEDs). We are therefore reviewing various types of cyclometalating chelates for which the favorable metal–chelate bonding interaction, on the one hand, makes the resulting phosphorescent complexes highly emissive in both fluid and solid states at room temperature. On the other hand, fine adjustment of ligand-centered π–π* electronic transitions allows tuning of emission wavelength across the whole visible spectrum. The cyclometalating chelates are then classified according to types of cyclometalating groups, i.e. either aromatic C–H or azolic N–H fragment, and the adjacent donor fragment involved in the formation of metallacycles; the latter is an N-containing heterocycle, N-heterocyclic (NHC) carbene fragment or even diphenylphosphino group. These cyclometalating ligands are capable to react with heavy transition-metal elements, namely: Ru(II), Os(II), Ir(III) and Pt(II), to afford a variety of highly emissive phosphors, for which the photophysical properties as a function of chelate or metal characteristics are systematically discussed. Using Ir(III) complexes as examples, the C^N chelates possessing both C–H site and N-heterocyclic donor group are essential for obtaining phosphors with emission ranging from sky-blue to saturated red, while the N^N chelates such as 2-pyridyl-C-linked azolates are found useful for serving as true-blue chromophores due to their increased ligand-centered π–π* energy gap. Lastly, the remaining NHC carbene and benzyl phosphine chelates are highly desirable to serve as ancillary chelates in localizing the electronic transition between the metal and remaining lower energy chromophoric chelates. As for the potential opto-electronic applications, many of them exhibit remarkable performance data, which are convincing to pave a broad avenue for further development of all types of phosphorescent displays and illumination devices (94 references).

Transition-metal phosphors with cyclometalating ligands: fundamentals and applications

Phosphorescence studies of a series of facial homoleptic cyclometalated iridium(III) complexes have been carried out. The complexes studied have the general structure Ir(III)(C−N)3, where (C−N) is a monoanionic cyclometalating ligand:  2-(5-methylthiophen-2-yl)pyridinato, 2-(thiophen-2-yl)-5-trifluoromethylpyridinato, 2,5-di(thiophen-2-yl)pyridinato, 2,5-di(5-methylthiophen-2-yl)pyridinato, 2-(benzo[b]thiophen-2-yl)pyridinato, 2-(9,9-dimethyl-9H-fluoren-2-yl)pyridinato, 1-phenylisoquinolinato, 1-(thiophen-2-yl)isoquinolinato, or 1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato. Luminescence properties of all the complexes at 298 K in toluene are as follows:  quantum yields of phosphorescence Φp = 0.08−0.29, emission peaks λmax = 558−652 nm, and emission lifetimes τ = 0.74−4.7 μs. Bathochromic shifts of the Ir(thpy)3 family [the complexes with 2-(thiophen-2-yl)pyridine derivatives] are observed by introducing appropriate substituents, e.g., methyl, trifluoromethyl, or thiophen-2-yl. However, Φp of the red em...

Homoleptic cyclometalated iridium complexes with highly efficient red phosphorescence and application to organic light-emitting diode.

The synthesis, structures, electrochemistry, and photophysics of a series of facial (fac) and meridional (mer) tris-cyclometalated Ir(III) complexes are reported. The complexes have the general formula Ir(C'N)(3) [where C'N is a monoanionic cyclometalating ligand; 2-phenylpyridyl (ppy), 2-(p-tolyl)pyridyl (tpy), 2-(4,6-difluorophenyl)pyridyl (46dfppy), 1-phenylpyrazolyl (ppz), 1-(4,6-difluorophenyl)pyrazolyl (46dfppz), or 1-(4-trifluoromethylphenyl)pyrazolyl (tfmppz)]. Reaction of the dichloro-bridged dimers [(C'N(2)Ir(mu-Cl)(2)Ir(C'N)(2)] with 2 equiv of HC( wedge )N at 140-150 degrees C forms the corresponding meridional isomer, while higher reaction temperatures give predominantly the facial isomer. Both facial and meridional isomers can be obtained in good yield (>70%). The meridional isomer of Ir(tpy)(3) and facial and meridional isomers of Ir(ppz)(3) and Ir(tfmppz)(3) have been structurally characterized using X-ray crystallography. The facial isomers have near identical bond lengths (av Ir-C = 2.018 A, av Ir-N = 2.123 A) and angles. The three meridional isomers have the expected bond length alternations for the differing trans influences of phenyl and pyridyl/pyrazolyl ligands. Bonds that are trans to phenyl groups are longer (Ir-C av = 2.071 A, Ir-N av = 2.031 A) than when they are trans to heterocyclic groups. The Ir-C and Ir-N bonds with trans N and C, respectively, have bond lengths very similar to those observed for the corresponding facial isomers. DFT calculations of both the singlet (ground) and the triplet states of the compounds suggest that the HOMO levels are a mixture of Ir and ligand orbitals, while the LUMO is predominantly ligand-based. All of the complexes show reversible oxidation between 0.3 and 0.8 V, versus Fc/Fc(+). The meridional isomers are easier to oxidize by ca. 50-100 mV. The phenylpyridyl-based complexes have reduction potentials between -2.5 and -2.8 V, whereas the phenylpyrazolyl-based complexes exhibit no reduction up to the solvent limit of -3.0 V. All of the compounds have intense absorption bands in the UV region assigned into (1)(pi --> pi) transitions and weaker MLCT (metal-to-ligand charge transfer) transitions that extend to the visible region. The MLCT transitions of the pyrazolyl-based complexes are hypsochromically shifted relative to those of the pyridyl-based compounds. The phenylpyridyl-based Ir(III) tris-cyclometalates exhibit intense emission both at room temperature and at 77 K, whereas the phenylpyrazolyl-based derivatives emit strongly only at 77 K. The emission energies and lifetimes of the phenylpyridyl-based complexes (450-550 nm, 2-6 micros) and phenylpyrazolyl-based compounds (390-440 nm, 14-33 micros) are characteristic for a mixed ligand-centered/MLCT excited state. The meridional isomers for both pyridyl and pyrazolyl-based cyclometalates show markedly different spectroscopic properties than do the facial forms. Isolated samples of mer-Ir(C( wedge )N)(3) complexes can be thermally and photochemically converted to facial forms, indicating that the meridional isomers are kinetically favored products. The lower thermodynamic stabilities of the meridional isomers are likely related to structural features of these complexes; that is, the meridional configuration places strongly trans influencing phenyl groups opposite each other, whereas all three phenyl groups are opposite pyridyl or pyrazolyl groups in the facial complexes. The strong trans influence of the phenyl groups in the meridional isomers leads to the observation that they are easier to oxidize, exhibit broad, red-shifted emission, and have lower quantum efficiencies than their facial counterparts.

Synthesis and characterization of facial and meridional tris-cyclometalated iridium(III) complexes.

Cyclometalated complexes of platinum(II): homoleptic compounds with aromatic C,N ligands

Photochemical preparation of luminescent platinum(IV) complexes via oxidative addition on luminescent platinum(II) complexes.

The study of the photochemical and photophysical properties of transition metal complexes is of great interest for theoretical reasons (i.e., for a better understanding of the “excited state dimension” of chemistry) as well as for practical applications (luminescent materials, photocatalytic processes etc.). In the last few years the attention of numerous research groups has been focussed on the search and characterization of transition metal complexes that can play the role of light absorption sensitizers (LAS) and/or light emission sensitizers (LES) for the interconversion between light energy and chemical energy via electron transfer reactions involving electronically excited states (Balzani 1983). To perform systematic experiments in this field as well as to arrive at practical devices we need a series of compounds covering a broad range of excited state energies, lifetimes, and oxidation-reduction potentials. The family of Ru(II)-polypyridine compounds, having as a prototype the famous \({\text{R}\text{u} (\text{b}\text{p}\text{y})_3}^{2+}\) complex, has proved to be very interesting for these purposes, and some hundreds Ru(II)-polypyridine compounds have been synthetized and studied in the last few years (Kalyanasundaram; Juris). Polypyridine complexes of Cr(III) (Jamieson), Rh(III) (De Armond), Ir(III) (Watts), and Os(II) (Sutin) have also been studied, but an ideal LAS and/or LES has not yet been found (Balzani 1986).

L. Chassot

Papers

Cyclometalated complexes of platinum(II): homoleptic compounds with aromatic C,N ligands

Photochemical preparation of luminescent platinum(IV) complexes via oxidative addition on luminescent platinum(II) complexes.

On the Orbital Nature of the Luminescent Excited State of Orthometalated Transition Metal Complexes

Photochemical Preparation of Luminescent Platinum(IV) Complexes via Oxidative Addition on Luminescent Platinum(II) Complexes.

Cyclometalated Complexes of Platinum(II): Homoleptic Compounds with Aromatic C,N Ligands.