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Weak light absorption of common Ir(III) complexes (e. g., using phenylpyridine as the ligand) has hindered their applications in photocatalytic hydrogen generation from water as an efficient photosensitizer. To address this issue, a series of cyclometalated Ir(III) complexes (Ir1-Ir5), featuring different electron-donating substituents to enhance the absorptivity, have been synthesized and studied as photosensitizers (PSs) for light-driven hydrogen production from water. Ir6-Ir7 were prepared as fundamental systems for comparisons. Electron donors, including 9-phenylcarbazole, triphenylamine, 4,4'-dimethoxytriphenylamine, 4,4'-di(N-hexylcarbazole)triphenylamine moieties were introduced on 6-(thiophen-2-yl)phenanthridine-based cyclometalating (C^N) ligands to explore the donor effect on the hydrogen evolution performance of these cationic Ir(III) complexes. Remarkably, Ir4 with 4,4'-dimethoxytriphenylamine achieved the highest turn-over number (TON) of 12 300 and initial turnover frequency (TOF

Three molecular photosensitizers (PSs) with carboxylic acid anchors for attachment to platinized titanium dioxide nanoparticles were studied for light-driven hydrogen production from a fully aqueous medium with ascorbic acid (AA) as the sacrificial electron donor. Two zinc(II) porphyrin (ZnP)-based PSs were used to examine the effect of panchromatic sensitization on the photocatalytic H2 generation. A dyad molecular design was used to construct a difluoro boron-dipyrromethene (bodipy)-conjugated ZnP PS (ZnP-dyad), whereas the other one featured an electron-donating diarylamino moiety (YD2-o-C8). To probe the use of the ZnP scaffold in this particular energy conversion process, an organic PS without the ZnP moiety (Bodipy-dye) was also synthesized for comparison. Ultrafast transient absorption spectroscopy was adopted to map out the energy transfer processes occurring in the dyad and to establish the bodipy-based antenna effect. In particular, the systems with YD2-o-C8 and ZnP-dyad achieved a remarkable initial activity for the production of H2 with an initial turnover frequency (TOFi ) higher than 300 h-1 under white light irradiation. The use of ZnP PSs in dye-sensitized photocatalysis for the H2 evolution reaction in this study indicated the importance of the panchromatic sensitization capability for the development of light absorbing PSs.

A new building block ATVTA that uses stiff carbon-carbon triple bonds (A) on 1,2-di(2-thienyl)-ethene (TVT) has been developed. Oligothiophene derivatives S-01 with a TVT unit, S-02 with a 5,5'-diethynyl-2,2'-dithienyl (AT2) unit and S-03 with ATVTA were synthesized to compare their effects in a systematic study. Due to the better π-conjugation extension of the TVT unit, S-01 exhibits the most red-shifted absorption profile among them, whereas S-02 possesses the deepest HOMO level. While the HOMO level of S-03 is down-shifted by 0.02 eV relative to that of S-01, the alkyne linkages can effectively down-shift the HOMO level. By replacing the terminal units of S-03 with stronger electron acceptors, S-04 and S-05 exhibited broader absorption profiles and lower HOMO levels than those of S-03. Organic solar cells based on these molecules were fabricated and an S-03:PC60 BM (1:1, w/w) based device afforded the highest Voc value of 0.96 V and a power conversion efficiency (PCE) of 2.19 %.

Two new organometallic copolymers (PVFVM1 and PVFVM1-1) bearing different molar ratios of ferrocene and triphenylamine pendants were successfully designed and synthesized as cathode active materials for organic-battery applications. Their structural and thermal characteristics were determined by 1H NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, size exclusion chromatography (SEC), and thermogravimetric analysis (TGA). Cyclic voltammograms of the as-prepared polymers show that the electrochemical reactions of the ferrocene and triphenylamine moieties are reversible after the first cycle. A composite electrode based on copolymer PVFVM1 exhibits an initial specific discharge capacity of 102 mA h g–1, which corresponds to 98 % of its theoretical capacity (104 mA h g–1). The cycle endurances for both polymers have been evaluated for over 50 cycles. Our results show that both copolymers are good candidates as a new class of cathode active materials and charge-storage materials for rechargeable batteries.

A series of purely organic small molecules 1-4 based on bis(arylene ethynylene)s with various electron-rich aromatic bridges, such as benzene, cyclopentadithiophene (CDT), and diphenyl(p-tolyl)amine, were synthesized by a Sonogashira coupling reaction. Their optical, electronic, and electrochemical properties were fully characterized. The photovoltaic properties of these molecules as donor materials and [6,6]-phenyl-C71 -butyric acid methyl ester as an acceptor material in solution-processed bulk heterojunction devices were studied. Among them, CDT-bridged molecule 2 exhibited the best photovoltaic performance and achieved a power conversion efficiency of 3.28 %. In addition, the photovoltaic efficiencies of these molecules are higher than their corresponding platinum-containing counterparts, probably owing to their stronger light absorption and improved open-circuit voltage.

New ruthenium(II) photosensitizers [Ru(dcbpy)(L)(NCS)2] (dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine; L = 4,4′-bis{di[4-(N,N′-dimethylamino)phenyl]amino}-2,2′-bipyridine (1), 4,4′-bis[di(4-methoxyphenyl)amino]-2,2′-bipyridine (2), and 4,4′-bis[di(4-tolyl)amino]-2,2′-bipyridine (3)) were prepared and characterized and their application in dye-sensitized solar cells is presented. The optical absorption of these photosensitizers gives a peak at around 540 nm, which is very similar to that of the standard N719. The maximum incident photon-to-current conversion efficiency (IPCE) of 80.6 % was obtained for 3, which corresponded to a power conversion efficiency (η) of 5.68 % under standard air mass (AM) 1.5 sunlight (versus N719 at 6.76 %). Molecular cosensitization of 3 with an organic dye, QS-DPP-I, yielded higher η values up to 6 % relative to the cells based on individual photosensitizers, and the corresponding IPCE can reach 93.6 % at 549 nm. A preliminary stability test of the devices was also conducted.

New heteroleptic cyclometalated iridium(III) 2-phenylpyridine-type complexes with trifluoromethyl substituents and various main-group moieties were synthesized and their photophysical, electrochemical, and electroluminescent (EL) properties studied. The emission color can be tuned by a facile derivatization of the phenyl moiety of 2-phenylpyridine with various main-group moieties, and we have prepared new yellowishgreen to orange triplet emitters with enhanced charge injection/charge transporting features, which can furnish attractive EL performance in phosphorescent organic light-emitting devices (OLEDs). Attempts were also made to fabricate two-color white-light OLEDs based on a combination of fluorescent blue and phosphorescent orange emitters.

White polymer light-emitting devices (WPLEDs) have become a field of immense interest in both scientific and industrial communities. They have unique advantages such as low cost, light weight, ease of device fabrication, and large area manufacturing. Applications of WPLEDs for solid-state lighting are of special interest because about 20% of the generated electricity on the earth is consumed by lighting. To date, incandescent light bulbs (with a typical power efficiency of 12-17 lm W(-1) ) and fluorescent lamps (about 40-70 lm W(-1) ) are the most widely used lighting sources. However, incandescent light bulbs convert 90% of their consumed power into heat while fluorescent lamps contain a small but significant amount of toxic mercury in the tube, which complicates an environmentally friendly disposal. Remarkably, the device performances of WPLEDs have recently been demonstrated to be as efficient as those of fluorescent lamps. Here, we summarize the recent advances in WPLEDs with special attention paid to the design of novel luminescent dopants and device structures. Such advancements minimize the gap (for both efficiency and stability) from other lighting sources such as fluorescent lamps, light-emitting diodes based on inorganic semiconductors, and vacuum-deposited small-molecular devices, thus rendering WPLEDs equally competitive as these counterparts currently in use for illumination purposes.

Hard ferromagnetic (L10 phase) FePt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are considered to be one of the most promising candidates for the next generation of ultrahigh-density data storage system. The question of how to generate ordered patterns of L10-FePt NPs and how to transform the technology for practical applications represents a key current challenge. Here the direct synthesis of L10 phase FePt NPs by pyrolysis of Fe-containing and Pt-containing metallopolymer blend without post-annealing treatment is reported. Rapid single-step fabrication of large-area nanodot arrays (periodicity of 500 nm) of L10-ordered FePt NPs can also be achieved by employing the metallopolymer blend, which possesses excellent solubility in most organic solvents and good solution processability, as the precursor through nanoimprint lithography (NIL). Magnetic force microscopy (MFM) imaging of the nanodot pattern indicates that the patterned L10 phase FePt NPs are capable of exhibiting decent magnetic response, which suggests a great potential to be utilized directly in the fabrication of bit patterned media (BPM) for the next generation of magnetic recording technology.

A new series of conjugated oligothiophene-bridged bis(arylene ethynylene) small molecules have been designed, synthesized, and characterized by photophysical, electrochemical and computational methods. These compounds were found to have optimal LUMO levels that ensure effective charge transfer from these compounds to [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM). They were utilized as good electron-donor materials that can be blended with electron-acceptor PC70BM in the fabrication of solution-processed molecular bulk heterojunction (BHJ) solar cells. All of these BHJ devices showed very high open-circuit voltage (V(oc)) of 0.90-0.97 V, and the best power conversion efficiency achieved was 3.68%. The high V(oc) is consistent with the deeper low-lying HOMO level and is relatively insensitive to the donor : acceptor blend ratio. The spin-coated thin films of these small molecules showed p-channel field-effect charge transport with the hole mobilities of up to 2.04×10(-4) cm(2) V(-1) s(-1). These compounds illuminate the potential of solution-processible small-molecular aryl acetylide compounds for efficient power generation in photovoltaic implementation.

Insertion of transition metal elements into organic polymeric scaffolds enables a nice coupling of the intriguing physical traits of metal complexes such as electronic, optical and magnetic properties with the solution processability of carbon-based macromolecules. The propensity of these metal-based polymers towards exhibiting metal–metal interactions can also provide additional means for manipulating the structural order and electronic coupling in the molecules. Among these metallopolymers, rigid-rod transition metal σ-acetylide polymers, or polymetallaynes in short, are of much current interest. These organometallic polymers are important functional materials showing unique characteristics including electrical semiconductivity, photo-/electroluminescence, non-linear optical properties, liquid crystallinity, chemosensing capability and photovoltaic effect. Recently, there has been an impressive progress of functional polymetallaynes consisting of a variety of conjugated organic bridging moieties and transition metals. In this review, we summarize the structure–property–function relationships of polymetallaynes of different transition metals, with a major focus on the effect of transition metals and the structural modification of ligands in activating their multifunctional properties. Different emerging applications can thus be realized, for example, as the converters for both light/electricity signals, sensor protectors against intense laser beam and patternable precursors to magnetic metal alloy nanoparticles for data storage, etc.

We have studied the properties of organic and organometallic polymers based on a similar chemical structure to elucidate the influence of the metal center on the optical and electronic properties of the polymers as well as their photovoltaic performance. Detailed characterization of the optical properties of both polymers is performed and film morphology and photovoltaic performance are compared. Metal-containing polymers exhibit red-shifted absorption and under optimal processing conditions exhibit different film morphology compared with the metal-free ones. Our results indicate that organometallic polymers represent a promising class of compounds for improved performance in photovoltaic cells.

An extremely high-efficiency solution-processed white organic light-emitting diode (WOLED) is successfully developed by simultaneously using an ideal dendritic host material and a novel efficient orange phosphorescent iridium complex. The optimized device exhibits forward-viewing efficiencies of 70.6 cd A(-1) , 26.0%, and 47.6 lm W(-1) at a luminance of 100 cd m(-2) , respectively, promising the low-cost solution-processed WOLEDs a bright future as the next generation of illumination sources.

Two novel covalently-linked organic-inorganic hybrid compounds [(n-C4H9)4N]2[Mo6O18{≡N–(2-Np)}] (NA–Mo6) and [(n-C4H9)4N]2[Mo6O17{≡N–(1-Np)}2] (NA2–Mo6) (2-Np = 2-naphthyl; 1-Np = 1-naphthyl) have been prepared by the reaction of 2-naphthylamine (2-NpNH2) or 1-naphthylamine (1-NpNH2) with [(n-C4H9)4N]2[Mo6O19] (Mo6) in the presence of N,N′-dicyclohexylcarbodiimide (DCC) in anhydrous acetonitrile, and have been characterized by 1H NMR, IR, UV/Vis, and fluorescence spectra as well as X-ray crystallography. Structural analyses reveal the formation of self-assembled infinite 1-D and 3-D supramolecular frameworks. The UV/Vis spectra of NA–Mo6 and NA2–Mo6 show that the lowest energy electronic transfers occur at 362 and 394 nm, respectively, which are dramatically red-shifted when compared to that of Mo6. The luminescence studies show that Mo6 can notably quench the emission of naphthylamine. Monolayer and multilayer films of NA–Mo6 and NA2–Mo6 were fabricated on different substrates by the Langmuir–Blodgett (LB) technique using H2O as the subphase. For comparison, another two types of organic-inorganic hybrid films composed of noncovalently-linked 1-NpNH2/Mo6 and 2-NpNH2/Mo6 systems were also deposited onto the same substrates under the same conditions by the LB technique using an aqueous solution of Mo6 as the subphase. The as-prepared organic-inorganic hybrid films were characterized by π-A isotherms, UV/Vis absorption spectra, photoluminescence spectra, and scanning tunneling microscopy. The results indicate that stable monolayers can be formed at the air–water interface for NA–Mo6 and NA2–Mo6, and at the air–Mo6 solution interface for 1-NpNH2 and 2-NpNH2. The four LB films containing NA–Mo6, NA2–Mo6, 1-NpNH2/Mo6, and 2-NpNH2/Mo6 display interesting electrical conductivity.

A homologous set of 9,9-dialkyl-4,5-diazafluorene compounds were prepared by alkylation of 4,5-diazafluorene with the appropriate alkyl bromide and under basic conditions. The structures of these simple organic compounds were confirmed by spectroscopic techniques (FTIR, NMR, and FABMS). Their biological effects toward a panel of human carcinoma cells, including Hep3B hepatocellular carcinoma, MDAMB-231 breast carcinoma, and SKHep-1 hepatoma cells, were investigated; a structure-activity correlation was established with respect to the length of the alkyl chain and the fluorene ring structure. The relationship between the mean potency [log(1/IC(50))] and alkyl chain length was systematically studied. The results show that compounds with butyl, hexyl, and octyl chains exhibit good growth inhibitory effects toward these three human carcinoma cell lines, and the 9,9-dihexyl-4,5-diazafluorene further exhibits antitumor activity in athymic nude mice Hep3B xenograft models. For the structurally related dialkylfluorenes that lack the diaza functionality, in vitro cytotoxicity was not observed at clinically relevant concentrations.

Phosphorus-bridged strained [1]ferrocenophanes [Fe{(eta-C(5)H(4))(2)P(CH(2)CMe(3))}] (2) and [Fe{(eta-C(5)H(4))(2)P(CH(2)SiMe(3))}] (3) with neopentyl and (trimethylsilyl)methyl substituents on phosphorus, respectively, have been synthesized and characterized. Photocontrolled living anionic ring-opening polymerization (ROP) of the known phosphorus-bridged [1]ferrocenophane [Fe{(eta-C(5)H(4))(2)P(CMe(3))}] (1) and the new monomers 2 and 3, initiated by Na[C(5)H(5)] in THF at 5 degrees C, yielded well-defined polyferrocenylphosphines (PFPs), [Fe{(eta-C(5)H(4))(2)PR}](n) (R=CMe(3) (4), CH(2)CMe(3) (5), and CH(2)SiMe(3) (6)), with controlled molecular weights (up to ca. 60 x 10(3) Da) and narrow molecular weight distributions. The PFPs 4-6 were characterized by multinuclear NMR spectroscopy, DSC, and by GPC analysis of the corresponding poly(ferrocenylphosphine sulfides) obtained by sulfurization of the phosphorus(III) centers. The living nature of the photocontrolled anionic ROP allowed the synthesis of well-defined all-organometallic PFP-b-PFS(F) (7a and 7b) (PFS(F)=polyferrocenylmethyl(3,3,3,-trifluoropropyl)silane) diblock copolymers through sequential monomer addition. TEM studies of the thin films of the diblock copolymer 7b showed microphase separation to form cylindrical PFS(F) domains in a PFP matrix.

The synthesis, thermal and emission properties of an electrophosphorescent platinum(II) metallopolyyne polymer consisting of 9-butylcarbazole-2,7-diyl spacer P1 are described. The optical and electronic properties of P1 are compared to their molecular diplatinum(II) and digold(I) model complexes. The photophysical properties of P1 are somehow analogous to its 2,7-fluorene-linked congener but differs significantly from that for the 3,6-carbazole derivative. Its optical band gap is notably reduced as compared to that for the 3,6-carbazole analog. Multi-layer polymer light-emitting diodes (PLEDs) were fabricated with P1 as the emitting layer which gave a strong green-yellow electrophosphorescence. The best PLED can reach the maximum current efficiency of 4.7 cd . A(-1) at 5 wt.-% doping level, corresponding to an external quantum efficiency of 1.5%. This represents the first literature example of efficient PLEDs exhibiting pure triplet emission under electrical excitation for metallopolyynes without the concomitant singlet emission.

A series of solution-processable and strongly visible-light absorbing polyplatinynes containing oligothienyl–fluorene ring hybrids were synthesized and characterized. These rigid-rod organometallic materials are soluble in polar organic solvents and show intense absorptions in the visible spectral region, rendering them excellent candidates for bulk heterojunction polymer solar cells. The photovoltaic behavior depends significantly on the number of thienyl rings along the polymer chain, and some of these polymer solar cells show high power conversion efficiencies (PCEs) of up to 2.9% and a peak external quantum efficiency to 83% under AM1.5 simulated solar illumination. The effect of oligothienyl chain length on improving the polymer solar cell efficiency and on their optical and charge transport properties is elucidated in detail. At the same blend ratio of 1:5, the light-harvesting capability and PCE increase markedly with increasing number of thienyl rings. The power dependencies of the solar cell parameters (including the short-circuit current density, open-circuit voltage, fill-factor, and PCE) were also examined. The present work opens up an attractive avenue to developing conjugated metallopolymers with broad and strong solar energy absorptions and tunable solar cell efficiency and supports the potential of metalated conjugated polymers for efficient power generation.

The synthesis of polymers of the type (-Cz-C[triple chemical bond]C-PtL(2)-C[triple chemical bond]C-Cz-X-)(n) along with the corresponding model compounds (Ph-PtL'(2)-C[triple chemical bond]C-Cz)(2)-X-, where Cz=3,3'-carbazole, X=nothing, Cz, or F (2,2'-fluorene), L=PBu(3), and L'=PEt(3) are reported. The electronic spectra (absorption, excitation, emission, and ns-transient spectra) and the photophysics of these species in 2-methyltetrahyrofuran (2MeTHF) at 298 and 77 K are presented. Evidence for singlet electron and triplet energy transfer from the Cz chromophore to the F moiety are provided and discussed in detail. The rate for electron transfer is very fast (>4 x 10(11) s(-1)), whereas that for triplet-triplet energy transfer is much slower (approximately 10(3) s(-1)). This work represents a very rare example of studies that address electronic communication in the backbone of a conjugated organometallic polymer.

With the target to design and develop new functionalized green triplet light emitters that possess distinctive electronic properties for robust and highly efficient phosphorescent organic light-emitting diodes (PHOLEDs), a series of bluish-green to yellow-green phosphorescent tris-cyclometalated homoleptic iridium(III) complexes [Ir(ppy-X)(3)] (X=SiPh(3), GePh(3), NPh(2), POPh(2), OPh, SPh, SO(2)Ph, Hppy=2-phenylpyridine) have been synthesized and fully characterized by spectroscopic, redox, and photophysical methods. By chemically manipulating the lowest triplet-state character of Ir(ppy)(3) with some functional main-group 14-16 moieties on the phenyl ring of ppy, a new family of metallophosphors with high-emission quantum yields, short triplet-state lifetimes, and good hole-injection/hole-transporting or electron-injection/electron-transporting properties can be obtained. Remarkably, all of these Ir(III) complexes show outstanding electrophosphorescent performance in multilayer doped devices that surpass that of the state-of-the-art green-emitting dopant Ir(ppy)(3). The devices described herein can reach the maximum external quantum efficiency (eta(ext)) of 12.3 %, luminance efficiency (eta(L)) of 50.8 cd A(-1), power efficiency (eta(p)) of 36.9 Lm W(-1) for [Ir(ppy-SiPh(3))(3)], 13.9 %, 60.8 cd A(-1), 49.1 Lm W(-1) for [Ir(ppy-NPh(2))(3)], and 10.1 %, 37.6 cd A(-1), 26.1 Lm W(-1) for [Ir(ppy-SO(2)Ph)(3)]. These results provide a completely new and effective strategy for carrier injection into the electrophosphor to afford high-performance PHOLEDs suitable for various display applications.

A new and synthetically versatile strategy has been developed for the phosphorescence color tuning of cyclometalated iridium phosphors by simple tailoring of the phenyl ring of ppy (Hppy=2-phenylpyridine) with various main-group moieties in [Ir(ppy-X)(2)(acac)] (X=B(Mes)(2), SiPh3, GePh3, NPh2, POPh2, OPh, SPh, SO2Ph). This can be achieved by shifting the charge-transfer character from the pyridyl groups in some traditional iridium ppy-type complexes to the electron-withdrawing main-group moieties and these assignments were supported by theoretical calculations.

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9-arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations. The highest occupied molecular orbital levels of these complexes are raised by the integration of a carbazole unit to the iridium isoquinoline core so that the hole-transporting ability is improved in the resulting complexes relative to those with I-phenylisoquinoline ligands. All of the complexes are highly thermally stable and emit an intense red light at room temperature with relatively short lifetimes that are beneficial for highly efficient organic light-emitting diodes (OLEDs).

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole-transporting carbazole and fluorene-based 2-phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the pi-conjugation through incorporation of electron- pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest oc- cupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium-based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo- and electroluminescence properties of these phosphorescent carbazolylfluorene-functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light-emitting diodes (OLEDs) using these complexes as the solution-processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole-transporting layer.I These orange-emitting devices can produce a maximum current efficiency of similar to 30 cd A(-1) corresponding to an external quantum efficiency of similar to 10 % ph/el (photons per electron) and a power efficiency of similar to 14 Im W-1.

In modern research on organic light-emitting diodes (OLEDs), cyclometalated iridium(III) complexes represent one of the most studied class of compounds. The high emission efficiency caused by the strong spin-orbit coupling in the presence of heavy metals leads to the mixing of singlet and triplet manifolds so that both the singlet and triplet excitons can be harvested. For OLEDs to be useful in displays application, true red, green, and blue emissions of sufficient luminous efficiencies and proper chromaticity are required. In recent years, the development of materials for phosphorescent red OLEDs has indeed gone through several important evolutional stages. However, the luminescent quantum yields of red-emitting iridium(III) phosphors tend to be intrinsically low which are governed by the energy gap law for triplet states in which the luminescence quantum yields tend to decrease with an increase in the emission wavelength. Many red organic dyes currently in use do not show a good compromise between device efficiency and color purity. In general, a dilemma facing red OLEDs was realized in which efficient and bright dopants are not red enough, and red-enough dopants are not efficient and bright. In this review article, we highlight the recent progress and current challenges of efficient OLEDs based on cyclometalated iridium(III) dyes which exhibit saturated red and near-infrared electroluminescence. Optimization of the phosphorescent red OLED efficiency/color purity trade-off and extension of the work to other organometallic phosphors are also presented and discussed.

Organic light-emitting devices (OLEDs) are on the lips of most electronic manufacturers currently. With good progress made in terms of production cost, efficiency and color output, OLEDs have found more applications recently as compared to those some years ago. Because of the possibility of obtaining long-lasting, durable and energy-efficient OLEDs, researchers devote much time and effort towards the improvement of OLED technology and development of advanced OLED products. Blue light-emitting materials, especially blue phosphorescent materials, are indispensable for full-color displays and white OLED lighting. Compared with green and red light-emitting materials and devices, the blue-emitting counterparts show a relatively inferior performance in terms of color purity, luminescence efficiency and device durability. In this perspective article, we highlight the recent progress and current challenges of blue-emitting metallophosphors based on small molecules and their applications in phosphorescent OLEDs.