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 pi-pi* 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 pi-pi* 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).

This article presents general concepts that have guided important developments in our recent research progress regarding room-temperature phosphorescent dyes and their potential applications. We first elaborate the theoretical background for emissive metal complexes and the strategic design of the chelating C-linked 2-pyridylazolate ligands, followed by their feasibility in functionalization and modification in an aim to fine-tune the chemical and photophysical properties. Subsequently, incorporation of 2-pyridylazolate chromophores is illustrated in the synthesis of the highly emissive, charge-neutral Os, Ru, Ir, and Pt complexes. Insights into their photophysical properties are gained from spectroscopy, relaxation dynamics, and theoretical approaches, from which the lowest-lying excited states, competitive radiative decay, and radiationless processes are then analyzed in detail. In view of applications, their potentials for OLEDs have been evaluated. The results, in combination with the fundamental basis, give a conceptual design contributed to the future advances in the field of OLEDs.

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Organic triplet-state light-emitting materials (organic phosphorophores) have been one of the most important recent developments in the field of organic light-emitting diodes (OLEDs).[1±4] Organic electrophosphorescent materials provided one of the major breakthroughs in electroluminescence efficiency, which is usually limited to an external quantum efficiency (EQE) of around 5 % for devices based on singletstate fluorescent materials. Owing to its thin-film, lightweight, fast-response, wide-viewing-angle, high-contrast, and low-power attributes, OLEDs promise to be one of the major flat- [16±20]However, the development of highly efficient blue-light-emitting phosphorescent emitters in OLEDs, indispensable for the realization of RGB full-color displays and WOLEDs, is still in its infancy, and blue-light-emitting phosphorescent EL performance lags far behind that of the green-or red-light emitters.One of the best known triplet-state blue-light emitters is iridium(III) bis(4,6-difluorophenylpyridinato)picolate (FIrpic, Scheme 1).[21±23] Although a reasonably good EQE of about 10 % (or 10 lm W ±1 ) has been reported, its blue-light emission was far from saturated, with 1931 Commission Internationale de L'Eclairage x,y coordinates (CIE x,y ) of (0.17, 0.34) [23] thatwere best characterized as cyan in color. The most recent, and probably only the second phosphorescent blue emitter of practical use, was iridium(III) bis(4¢,6¢-difluorophenylpyridinato)tetrakis(1-pyrazolyl) borate) (FIr6), [24] whose blue OLED showed EQEs of 9±10 % (or 11±14 lm W ±1 ), and whose bluecolor chromaticity had been considerably improved to CIE x,y = 0.16, 0.26. There are a couple of limitations in the usage of phosphorescence-based materials for OLEDs. Compared with the short emission lifetime (scale of nanoseconds) of fluorescent materials, the relatively long phosphorescence lifetimes (microseconds scale) of the iridium complexes may lead to dominant triplet±triplet (T 1 ±T 1 ) annihilation at high currents. Long emission lifetimes also cause a long range of exciton diffusion (> 100 nm) that could get quenched in the adjacent layers of materials in the OLED. Consequently, organic phosphorescent materials are often adopted as dopants dispersed in a suitable host material, usually of high bandgap energies and good carrier transport properties. Arylamino-containing organic substances are usually the host materials of choice to alleviate this situation. This has worked reasonably well for phosphorescent green-or red-light-emitting materials. However, it has been demonstrated that the energy differences in the triplet energies of host and guest materials are very important for the confinement of electro-generated triplet excitons on the dopant molecules.[22±28] In cases of triplet-state bluelight emitters, common arylamino-containing substances, such as 4,4¢-bis(9-carbazolyl)-2,2¢-biphenyl (CBP) simply do not have sufficient triplet-state energy for effective T 1 ±T 1 energy transfer; later, a structurally modified host molecule, 1,3-bis(9-carba...