Ultrafast Intersystem Crossing and Structural Dynamics of [Pt(ppy)(µ-tBu2pz)]2.

Intersystem crossing (ISC) rates of transition-metal complexes are determined by the complex interplay of a molecule's electronic and structural dynamics. To broaden our understanding of these key factors, we investigate the case of the prototypical d8-d8 dimetal complex [Pt(ppy)(µ-tBu2pz)]2 using broad-band transient absorption anisotropy in combination with ultrafast fluorescence up-conversion and ab initio calculations. We find that, upon excitation of the molecule's metal-metal-to-ligand charge-transfer transition, ISC occurs in hundreds of femtoseconds from the lowest excited singlet state S1 to the triplet state T2, from where the energy relaxes to the lowest energy triplet state T1. ISC to the T2 state, rather than T1, is further rationalized through supporting arguments. Observed vibrational coherences along the Pt-Pt mode are attributed to the formation of nuclear wavepackets on the ground and excited electronic states that dephase prior to ISC because of the structural flexibility of the complex. Beyond demonstrating the relationship between the energy relaxation and structural dynamics of [Pt(ppy)(µ-tBu2pz)]2, our results provide new insights into the photoinduced dynamics of d8-d8 dimetal complexes more generally.

Synthesis and Characterization of a Series of Bis-homoleptic Cycloruthenates with Terdentate Ligands as a Family of Panchromatic Dyes.

A series of six homoleptic bis-cyclometalated ruthenium complexes, Ru(N^N^C)2, is reported where N^N^C is a 6-(2,4-difluoro-3-R3-phenyl)-4-R2-4'-R1-2,2'-bipyridine with R3 = -H or -CF3 and R2 and R1 = -COOEt or -CF3. An effective synthesis of the ligands and the complexes is described. The UV-visible absorption studies demonstrate that these complexes are panchromatic dyes absorbing up to 900 nm. Importantly, the onset of absorption depends only on the substitution on the metalated phenyl, whereas the intensity of absorption throughout the spectra is a function of substituents on both the phenyl and the bipyridine moieties. The same trend is observed in electrochemistry as the redox gap depends only on the substitution on the metalated phenyl, whereas the oxidation and reduction potentials are a function of substituents on both the phenyl and the bipyridine moieties. Preliminary tests as sensitizer for dye-sensitized solar cells demonstrate that the number of anchoring groups on the dye has a major influence on the device efficiency.

Tris-heteroleptic Iridium Complexes Based on Cyclometalated Ligands with Different Cores.

A series of tris-heteroleptic iridium complexes of the form [Ir(C^N1)(C^N2)(acac)] combining 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dFppy), 1-phenylpyrazole (ppz), and 1-(2,4-difluorophenyl)pyrazole (dFppz) as the C^N ligands have been synthesized and fully characterized by NMR, X-ray crystallography, UV-vis absorption and emission spectroscopy, and electrochemical methods. It is shown that "static properties" (e.g., absorption and emission spectra and redox potentials) are primarily dictated by the overall architecture of the complex, while "dynamic properties" (e.g., excited-state lifetime and radiative and nonradiative rate constants) are, in addition, sensitive to the specific positioning of the substituents. As a result, the two complexes [Ir(dFppy)(ppz)(acac)] and [Ir(ppy)(dFppz)(acac)] have the same emission maxima and redox potentials, but their radiative and nonradiative rate constants differ significantly by a factor ∼2. Then acetylacetonate (acac) was replaced by picolinate (pic), and two pairs of diastereoisomers were obtained. As expected, the use of pic as the ancillary ligand results in blue-shifted emission, stabilization of the oxidation potential, and improvement of the photoluminescence quantum yield, and only minor differences in the optoelectronic properties are found between the two diastereoisomers of each pair.

Blue and Green Phosphorescent Liquid-Crystalline Iridium Complexes with High Hole Mobility.

Blue- and green-emitting cyclometalated liquid-crystalline iridium complexes are realized by using a modular strategy based on strongly mesogenic groups attached to an acetylacetonate ancillary ligand. The cyclometalated ligand dictates the photophysical properties of the materials, which are identical to those of the parent complexes. High hole mobilities, up to 0.004 cm(2) V(-1) s(-1), were achieved after thermal annealing, while amorphous materials show hole mobilities of only approximately 10(-7) -10(-6) cm(2) V(-1) s(-1), similar to simple iridium complexes. The design strategy allows the facile preparation of phosphorescent liquid-crystalline complexes with fine-tuned photophysical properties.

High performance optical oxygen sensors based on iridium complexes exhibiting interchromophore energy shuttling.

A doubly pyrene-grafted bis-cyclometallated iridium complex with engineered electronically excited states demonstrates reversible electronic energy transfer between adjacent chromophores giving rise to extremely long-lived red luminescence in solution (τ = 480 µs). Time-resolved spectroscopic studies afforded determination of pertinent photophysical parameters including rates of energy transfer and energy distribution between constituent chromophores in the equilibrated excited molecule (ca. 98% on the organic chromophores). Incorporation into a nanostructured metal-oxide matrix (AP200/19) gave highly sensitive O2 sensing films, as the detection sensitivity was 200-300% higher than with the commonly used PtTFPP and approaches the sensitivity of the best O2-sensing dyes reported to date.

UV-visible Absorption Study of the Self-association of Non-ionic Chromonic Triphenylenes TP6EOnM (n = 2, 3, 4) in Dilute Aqueous Solutions: Impact of Chain Length on Aggregation.

A series of triphenylenes with oligoethoxy chains of various length, TP6EOnM with n = 2, 3, 4, has been synthesised and purified by HPLC. The self-association of these disc-shaped molecules in dilute aqueous solutions (∼10(-7) to ∼4 × 10(-4) M) has been studied by UV-visible absorption spectroscopy. The free energy of association decreases as the length of the chains increases. As a result, for a given concentration, the average size of aggregate diminishes as the chain length increases. While the absorption properties of the monomer are identical for the three molecules, the extinction coefficients of solutions of the three triphenylenes at a given concentration are significantly different and are directly linked to the average size of the aggregates. The change of epsilon values upon aggregation could explain the trend generally observed with dyes for solar cells substituted with chains of increasing length showing increasing extinction coefficient values.

Direct observation of reversible electronic energy transfer involving an iridium center.

A cyclometalated iridium complex is reported where the core complex comprises naphthylpyridine as the main ligand and the ancillary 2,2'-bipyridine ligand is attached to a pyrene unit by a short alkyl bridge. To obtain the complex with satisfactory purity, it was necessary to modify the standard synthesis (direct reaction of the ancillary ligand with the chloro-bridged iridium dimer) to a method harnessing an intermediate tetramethylheptanolate-based complex, which was subjected to acid-promoted removal of the ancillary ligand and subsequent complexation. The photophysical behavior of the bichromophoric complex and a model complex without the pendant pyrene were studied using steady-state and time-resolved spectroscopies. Reversible electronic energy transfer (REET) is demonstrated, uniquely with an emissive cyclometalated iridium center and an adjacent organic chromophore. After excited-state equilibration is established (5 ns) as a result of REET, extremely long luminescence lifetimes of up to 225 µs result, compared to 8.3 µs for the model complex, without diminishing the emission quantum yield. As a result, remarkably high oxygen sensitivity is observed in both solution and polymeric matrices.

High performance optical sensing nanocomposites for low and ultra-low oxygen concentrations using phase-shift measurements.

The accurate and real-time measurement of low and ultra-low concentrations of oxygen using non-invasive methods is a necessity for a multitude of applications, from brewing beer to developing encapsulating barriers for optoelectronic devices. Current optical methods and sensing materials often lack the necessary sensitivity, signal intensity, or stability for practical applications. In this report we present a new optical sensing nanocomposite resulting in an outstanding overall performance when combined with the phase-shift measurement method (determination of luminescence lifetime in the frequency domain). For the first time we have incorporated the standard PtTFPP dye (PtTFPP = platinum(II) 5,10,15,20-meso-tetrakis-(2,3,4,5,6-pentafluorophenyl)-porphyrin) into AP200/19, a nanostructured aluminium oxide-hydroxide solid support. This sensing film shows an excellent sensitivity between 0 and 1% O2 (KSV = 3102 ± 132 bar⁻¹) and between 0 and 10% O2 (KSV = 2568 ± 614 bar⁻¹) as well as Δτ0.05% (62.53 ± 3.66%), which makes it 62 times more sensitive than PtTFPP immobilized in polystyrene and also 8 times more sensitive than PtTFPP immobilized on silica beads. Furthermore the phase-shift measurement method results in a significant improvement (about 23 times) in stability compared to the use of intensity recording methods. The film also displays full reversibility, long shelf stability (no change observed after 12 months), and it is not affected by humidity. To establish this sensing methodology and develop sensors over the full range of the visible light, we also studied three other dye-AP200/19 nanocomposites based on phosphorescent cyclometalated iridium(III) complexes.

Charged bis-cyclometalated iridium(III) complexes with carbene-based ancillary ligands.

Charged cyclometalated (C(^)N) iridium(III) complexes with carbene-based ancillary ligands are a promising family of deep-blue phosphorescent compounds. Their emission properties are controlled primarily by the main C(^)N ligands, in contrast to the classical design of charged complexes where N(^)N ancillary ligands with low-energy π* orbitals, such as 2,2'-bipyridine, are generally used for this purpose. Herein we report two series of charged iridium complexes with various carbene-based ancillary ligands. In the first series the C(^)N ligand is 2-phenylpyridine, whereas in the second one it is 2-(2,4-difluorophenyl)-pyridine. One bis-carbene (:C(^)C:) and four different pyridine-carbene (N(^)C:) chelators are used as bidentate ancillary ligands in each series. Synthesis, X-ray crystal structures, and photophysical and electrochemical properties of the two series of complexes are described. At room temperature, the :C(^)C: complexes show much larger photoluminescence quantum yields (ΦPL) of ca. 30%, compared to the N(^)C: analogues (around 1%). On the contrary, all of the investigated complexes are bright emitters in the solid state both at room temperature (1% poly(methyl methacrylate) matrix, ΦPL 30-60%) and at 77 K. Density functional theory calculations are used to rationalize the differences in the photophysical behavior observed upon change of the ancillary ligands. The N(^)C:-type complexes possess a low-lying triplet metal-centered ((3)MC) state mainly deactivating the excited state through nonradiative processes; in contrast, no such state is present for the :C(^)C: analogues. This finding is supported by temperature-dependent excited-state lifetime measurements made on representative N(^)C: and :C(^)C: complexes.

Subnanometer Ga2O3 tunnelling layer by atomic layer deposition to achieve 1.1 V open-circuit potential in dye-sensitized solar cells.

Herein, we present the first use of a gallium oxide tunnelling layer to significantly reduce electron recombination in dye-sensitized solar cells (DSC). The subnanometer coating is achieved using atomic layer deposition (ALD) and leading to a new DSC record open-circuit potential of 1.1 V with state-of-the-art organic D-π-A sensitizer and cobalt redox mediator. After ALD of only a few angstroms of Ga(2)O(3), the electron back reaction is reduced by more than an order of magnitude, while charge collection efficiency and fill factor are increased by 30% and 15%, respectively. The photogenerated exciton separation processes of electron injection into the TiO(2) conduction band and the hole injection into the electrolyte are characterized in detail.

Influence of halogen atoms on a homologous series of bis-cyclometalated iridium(III) complexes.

A series of homologous bis-cyclometalated iridium(III) complexes Ir(2,4-di-X-phenyl-pyridine)(2)(picolinate) (X = H, F, Cl, Br) HIrPic, FIrPic, ClIrPic, and BrIrPic has been synthesized and characterized by NMR, X-ray crystallography, UV-vis absorption and emission spectroscopy, and electrochemical methods. The addition of halogen substituents results in the emission being localized on the main cyclometalated ligand. In addition, halogen substitution induces a blue shift of the emission maxima, especially in the case of the fluoro-based analogue but less pronounced for chlorine and bromine substituents. Supported by ground and excited state theoretical calculations, we rationalized this effect in a simple manner by taking into account the σp and σm Hammett constants on both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels. Furthermore, in comparison with FIrPic and ClIrPic, the impact of the large bromine atom remarkably decreases the photoluminescence quantum yield of BrIrPic and switches the corresponding lifetime from mono to biexponential decay. We performed theoretical calculations based on linear-response time-dependent density functional theory (LR-TDDFT) including spin-orbit coupling (SOC), and unrestricted DFT (U-DFT) to obtain information about the absorption and emission processes and to gain insight into the reasons behind this remarkable change in photophysical properties along the homologous series of complexes. According to theoretical geometries for the lowest triplet state, the large halogen substituents contribute to sizable distortions of specific phenylpyridine ligands for ClIrPic and BrIrPic, which are likely to play a role in the emissive and nonradiative properties when coupled with the heavy-atom effect.

Acid-induced degradation of phosphorescent dopants for OLEDs and its application to the synthesis of tris-heteroleptic iridium(III) bis-cyclometalated complexes.

Investigations of blue phosphorescent organic light emitting diodes (OLEDs) based on [Ir(2-(2,4-difluorophenyl)pyridine)(2)(picolinate)] (FIrPic) have pointed to the cleavage of the picolinate as a possible reason for device instability. We reproduced the loss of picolinate and acetylacetonate ancillary ligands in solution by the addition of Brønsted or Lewis acids. When hydrochloric acid is added to a solution of a [Ir(C^N)(2)(X^O)] complex (C^N = 2-phenylpyridine (ppy) or 2-(2,4-difluorophenyl)pyridine (diFppy) and X^O = picolinate (pic) or acetylacetonate (acac)), the cleavage of the ancillary ligand results in the direct formation of the chloro-bridged iridium(III) dimer [{Ir(C^N)(2)(µ-Cl)}(2)]. When triflic acid or boron trifluoride are used, a source of chloride (here tetrabutylammonium chloride) is added to obtain the same chloro-bridged iridium(III) dimer. Then, we advantageously used this degradation reaction for the efficient synthesis of tris-heteroleptic cyclometalated iridium(III) complexes [Ir(C^N(1))(C^N(2))(L)], a family of cyclometalated complexes otherwise challenging to prepare. We used an iridium(I) complex, [{Ir(COD)(µ-Cl)}(2)], and a stoichiometric amount of two different C^N ligands (C^N(1) = ppy; C^N(2) = diFppy) as starting materials for the swift preparation of the chloro-bridged iridium(III) dimers. After reacting the mixture with acetylacetonate and subsequent purification, the tris-heteroleptic complex [Ir(ppy)(diFppy)(acac)] could be isolated with good yield from the crude containing as well the bis-heteroleptic complexes [Ir(ppy)(2)(acac)] and [Ir(diFppy)(2)(acac)]. Reaction of the tris-heteroleptic acac complex with hydrochloric acid gives pure heteroleptic chloro-bridged iridium dimer [{Ir(ppy)(diFppy)(µ-Cl)}(2)], which can be used as starting material for the preparation of a new tris-heteroleptic iridium(III) complex based on these two C^N ligands. Finally, we use DFT/LR-TDDFT to rationalize the impact of the two different C^N ligands on the observed photophysical and electrochemical properties.

Bright blue phosphorescence from cationic bis-cyclometalated iridium(III) isocyanide complexes.

We report new bis-cyclometalated cationic iridium(III) complexes [(C(^)N)(2)Ir(CN-tert-Bu)(2)](CF(3)SO(3)) that have tert-butyl isocyanides as neutral auxiliary ligands and 2-phenylpyridine or 2-(4'-fluorophenyl)-R-pyridines (where R is 4-methoxy, 4-tert-butyl, or5-trifluoromethyl) as C(^)N ligands. The complexes are white or pale yellow solids that show irreversible reduction and oxidation processes and have a large electrochemical gap of 3.58-3.83 V. They emit blue or blue-green phosphorescence in liquid/solid solutions from a cyclometalating-ligand-centered excited state. Their emission spectra show vibronic structure with the highest-energy luminescence peak at 440-459 nm. The corresponding quantum yields and observed excited-state lifetimes are up to 76% and 46 µs, respectively, and the calculated radiative lifetimes are in the range of 46-82 µs. In solution, the photophysical properties of the complexes are solvent-independent, and their emission color is tuned by variation of the substituents in the cyclometalating ligand. For most of the complexes, an emission color red shift occurs in going from solution to neat solids. However, the shift is minimal for the complexes with bulky tert-butyl or trifluoromethyl groups on the cyclometalating ligands that prevent aggregation. We report the first example of an iridium(III) isocyanide complex that emits blue phosphorescence not only in solution but also as a neat solid.

A new generation of platinum and iodine free efficient dye-sensitized solar cells.

We report a series of cobalt complexes with various polypyridyl ligands, where the oxidation potential is tuned from 0.17 to 0.34 V vs. ferrocene. The highest occupied molecular orbitals (HOMO) of the cobalt complexes were stabilized by adding electron acceptor groups on pyridyl or replacing pyridyl by pyrazole. These complexes are then used as one-electron redox mediators in dye sensitized solar cells (DSSCs) together with polymer based cathode resulting in an excellent performance. The performance of DSSCs using the molecularly engineered cobalt redox shuttle and poly(3,4-alkylthiophenes) based cathode is better than the triiodide/iodide redox shuttle with platinized cathode. The use of high surface area poly(3,4-propylenedioxythiophene) based nanoporous layers allows higher catalytic activity thus minimizing the electrode-electrolyte interface issues.

Tris(2-(1H-pyrazol-1-yl)pyridine)cobalt(III) as p-type dopant for organic semiconductors and its application in highly efficient solid-state dye-sensitized solar cells.

Chemical doping is an important strategy to alter the charge-transport properties of both molecular and polymeric organic semiconductors that find widespread application in organic electronic devices. We report on the use of a new class of Co(III) complexes as p-type dopants for triarylamine-based hole conductors such as spiro-MeOTAD and their application in solid-state dye-sensitized solar cells (ssDSCs). We show that the proposed compounds fulfill the requirements for this application and that the discussed strategy is promising for tuning the conductivity of spiro-MeOTAD in ssDSCs, without having to rely on the commonly employed photo-doping. By using a recently developed high molar extinction coefficient organic D-π-A sensitizer and p-doped spiro-MeOTAD as hole conductor, we achieved a record power conversion efficiency of 7.2%, measured under standard solar conditions (AM1.5G, 100 mW cm(-2)). We expect these promising new dopants to find widespread applications in organic electronics in general and photovoltaics in particular.

Incorporating multiple energy relay dyes in liquid dye-sensitized solar cells.

Panchromatic response is essential to increase the light-harvesting efficiency in solar conversion systems. Herein we show increased light harvesting from using multiple energy relay dyes inside dye-sensitized solar cells. Additional photoresponse from 400-590 nm matching the optical window of the zinc phthalocyanine sensitizer was observed due to Förster resonance energy transfer (FRET) from the two energy relay dyes to the sensitizing dye. The complementary absorption spectra of the energy relay dyes and high excitation transfer efficiencies result in a 35% increase in photovoltaic performance.

Cyclometalated iridium(III) complexes based on phenyl-imidazole ligand.

Phenyl-imidazole-based ligands with various substitution patterns have been used as the main ligand for heteroleptic bis-cyclometalated iridium complexes. Two series of complexes have been prepared and their photophysical and electrochemical properties were studied. The phosphorescence emission maxima range from about 490 to 590 nm, that is, from greenish-blue to orange. The first series is of the form Ir(L)2(acac) (L: a phenyl-imidazole based ligand; acac: acetylacetonate). In the first complex, 1a, L is 1,4,5-trimethyl-2-phenyl-1H-imidazole. Then, methyl groups are replaced with phenyl groups and chlorines are grafted on the cyclometalated phenyl ring. The second series is of the form Ir(4,5-dimethyl-1,2-diphenyl-1H-imidazole)2(La) (La: ancillary ligand being acetylacetonate, acac, N,N-dimethylamino-picolinate, NPic, picolinate, Pic, or 2-(diphenylphosphino)acetic acid, P). These series show that modifying the substitution pattern on the ligands can alter the photophysical and electrochemical properties of the complexes. Overall, we show that compared to complexes containing phenyl-pyridine ligands, highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) are more delocalized over the entire main ligand in complexes containing phenyl-imidazole. Contrary to expectations, when chlorine atoms are used as strong acceptor substituents on the orthometalated phenyl, a red shift of the emission is observed. This behavior has been rationalized using theoretical calculations on the excited state of the chloro-substituted complex 3a compared to the model 1a.

Dual-emitting Langmuir-Blodgett film-based organic light-emitting diodes.

Langmuir-Blodgett (LB) films containing alternating layers of the metallosurfactants bis(4,4'-tridecyl-2,2'-bipyridine)-(4,4'-dicarboxy-2,2'-bipyridine) ruthenium(II)-bis(chloride) (1) and bis[2-(2,4-difluorophenyl)pyridine](4,4'-dinonadecyl-2,2'-bipyridine)iridium(III) chloride (2) have been prepared. Langmuir monolayers at the air-water interface of 1 and 2 with different anions in the subphase have been characterized by pi-A compression isotherms and Brewster angle microscopy (BAM). The transferred LB films have been characterized by IR, UV-vis and emission spectroscopy, and atomic force microscopy (AFM). Electroluminescent devices formed by LB films containing alternating layers of these two molecules show dual emission by simple mixing of the two emitters in a single LB film, and by preparing two stacked configurations, in which a LB layer of the ruthenium complexes is deposited on top of a LB layer of the iridium complexes and the inverse situation. The color of the electroluminescence can be tuned by changing the thickness of each LB layer. Due to efficient hole blocking of a layer of the iridium complexes when deposited on top of the layer of ruthenium complexes, in that configuration the green emission of the iridium complexes is suppressed. In the opposite case, excitons are generated in both layers although most likely preferentially in the layer of the iridium complexes.

Sublimation not an innocent technique: a case of bis-cyclometalated iridium emitter for OLED.

Isomerization of a neutral bis-cyclometalated iridium(III) complex has been observed for the first time during the preparation of vacuum-processed organic light-emitting devices (OLEDs) and reproduced in solution. Isolation of the isomer revealed a cis organization of the two pyridine rings of the cyclometalating ligands. Photophysical studies show very similar emission properties of the two isomers. However, due to in situ isomerization, it is only possible to prepare vacuum-processed OLED devices having a mixture of isomers.