Enhancing the photoluminescence quantum yields of blue-emitting cationic iridium(III) complexes bearing bisphosphine ligands†

Herein we present a structure–property relationship study of thirteen cationic iridium(III) complexes of the form of [Ir(C^N)2(P^P)]PF6 in both solution and the solid state through systematic evaluation of six bisphosphine (P^P) ligands (xantphos, dpephos, dppe, Dppe, nixantphos and isopropxantphos). All of the complexes are sky-blue emissive, but their photoluminescence quantum yields (ΦPL) are generally low. However, strong and long-lived blue luminescence (λem = 471 nm; ΦPL = 52%; τe = 13.5 μs) can be obtained by combining the reduced bite angle of the 1,2-bis-diphenylphosphinoethene (dppe) chelate with the bulky 2-(4,6-difluorophenyl)-4-mesitylpyridinato (dFmesppy) cyclometalating ligand. To the best of our knowledge this is the highest ΦPL and the longest τe reported for cyclometalated iridium(III) complexes bearing bisphosphine ligands. Light-emitting electrochemical cells (LEECs) were fabricated using lead complexes from this study, however due in part to the irreversible electrochemistry, no functional LEEC was achieved. Organic light-emitting diodes were successfully fabricated but only attained maximum external quantum efficiencies of 0.25%.


Introduction
The expansion of low-cost and more efficient lighting sources based on phosphorescent materials is one of the greatest challenges of our century. 1In particular, iridium complexes have attracted much attention due to their relatively short-lived triplet excited states (τ e ) and high photoluminescence quantum yields (Φ PL ), which are crucial properties for emitters employed in organic light emitting diodes (OLEDs) or lightemitting electrochemical cells (LEECs). 2 In addition, due to the large variety of ligand families that are readily synthetically accessible, the emission color of iridium(III) complexes can be easily tuned across the entirety of the visible spectrum. 3In the last decade, despite the reports of many phosphorescent green and red emitters 4 having been synthesised, the design of highperformance blue-emitting materials remains a challenge. 5ecently, examples of sky-blue and deep-blue emitting cationic iridium complexes bearing biimidazole, 6 bis(NHC), 7 substituted triazole or tetrazole, 8 or pyrazolyl-pyridine 9 as ancillary ligands have been explored, but challenges still remain regarding efficiencies and stabilities of these emitters in devices. 10hus, there is still a demand for blue-emitting phosphors as emitters in lighting devices.

Synthesis
− salt following an anion metathesis reaction using NH 4 PF 6 .The purity of the complexes was confirmed by 1 H, 13 C, 19 F and 31 P NMR spectroscopy, HRMS and melting point analyses ( 1 H, 13 C, 31 P, 19 F-NMR and HRMS spectra are reported in the ESI †).HRMS analysis showed in each case the diagnostic molecular ion peak.The 31 P NMR spectra showed one singlet between −15 and −25 ppm, corresponding to the two magnetically equivalent phosphorous atoms in the P^P ligand and one septet at around −150 ppm, characteristic of the PF 6 anion.The 19 F NMR spectra for 4a, 4b, 3c, 4c showed two singlets between −105 and −110 ppm corresponding to the two fluorine atoms present on each C^N ligand and a doublet at around −70, −80 ppm, characteristic to the six magnetically equivalent fluorine atoms coupled to the phosphorous nucleus of the PF 6 anion.In addition, crystal structures of 1a, 2a, 4a, 1b, 4b, 1c, 3c, 4c, 1e, were obtained through single crystal X-ray analysis.

Crystal structures
Crystal structures of complexes 1a, 2a, 4a, 1b, 4b, 1c, 3c, 4c and 1e were obtained through X-ray diffraction studies.The structures of the Ir(III) complexes 1a, 1b and 1c are shown in Fig. 1, those of complexes 4a, 4b and 4c are shown in Fig. 2, whereas the remaining structures are reported in the ESI.† In all the structures, the iridium centre adopts a distortedoctahedral geometry, as expected, with the two nitrogen atoms of the C^N ligands mutually trans to each other, and the two phosphorous atoms of the P^P ligand disposed trans with respect to the carbon atoms of the C^N ligands.Both the Ir-C and Ir-N bond lengths fall in the range expected for [Ir-(C^N) 2 (L^L)] complexes (where L^L is any bidentate ligand), and the Ir-P bond lengths also fall into the range expected for [Ir(C^N) 2 (P^P)] complexes with two phosphorus donors (CSD version 5.36). 26Those complexes with a mesityl-functionalized C^N ligand (2a, 4a, 2b and 4c), all display the desired orthogonal orientation of the mesityl with respect to the pyridinato fragment The structures of 1b and 1e are closely related to those of the known structures of these complexes, 19a,c including the arrangement of the complexes themselves.The differences primarily arise from changes in packing and solvation.

Photophysical properties
The optoelectronic properties of complexes 1-4 have been investigated both in MeCN solution and in the solid state and are summarized in Table 1.The absorption spectra are shown in Fig. 3.The absorption spectra of all the complexes are characterized by two intense bands between 260 nm and 320 nm and a broad lower intensity band at around 360 nm.Similar to many other cationic iridium complexes of the form [Ir(C^N) 2 (P^P)] + found in the literature, 16c,d,18,19 the two higher energetic bands can be attributed to the spin-allowed 1 π → π* ligand centered ( 1 LC) transitions localized on the C^N ligands, while the broad bands at wavelengths longer than 350 nm can  be assigned to a mixture of spin-allowed and spin-forbidden metal-to-ligand charge transfer transitions ( 1 MLCT/ 3 MLCT).Indeed, as previously reported and predicted by TD-DFT calculations, 4a,27 spin-forbidden transitions directly to the triplet state are accessible in iridium(III) complexes due to the large spin-orbit coupling exhibited by the heavy iridium atom.The presence of the mesityl moiety in 2a, 4a, 2b, 4b, 2c and 4c leads to enhanced molar absorptivities in the UV region of the spectrum while also introducing a strongly absorbing shoulder at around 260-270 nm, the transition of which is assigned as 1 LC in nature.
Fig. 4 illustrates the normalized room temperate emission spectra of 1-4 upon photoexcitation into the 1 π → π* band (at 360 nm).Emission is blue to blue-green with emission maxima bunched between 460 nm and 510 nm.There are two distinct families of complexes based on their emission profiles.A structured vibronic emission profile is observed for b, c and d complexes (Fig. 4b) bearing one of dpephos, dppe and Dppe P^P ligands, which is indicative of a 3 LC excited state.3c,11,19b,28 The emission is less structured for 1a, 2a, 4a, 1f (Fig. 4a) bearing xantphos-type ancillary ligands, which impli-cates greater 3 MLCT character.19a,27a,e No emission was detected for complex 1e.
Incorporation of electron-withdrawing fluorine atoms on the C^N ligand promoted the expected stabilization of the frontier molecular orbitals and the blue-shift in the emission observed for complexes 4a, 4b, 4c and 3c compared with their fluorine-free congeners.3b,20b Despite only minute variations in the emission energy, remarkable modulation of both Φ PL and τ e could be obtained through choice of C^N and P^P ligands.Firstly, of the ppy-containing complexes the highest photoluminescence quantum yields arise from complexes using dppe as the ancillary ligand (cf.1c), where Φ PL at 4.2% is an order of magnitude higher than the other complexes in the series, save 1d.Bi-exponential decay kinetics were observed for each of these complexes, similar to other [Ir(C^N) 2 (P^P)] + complexes 19a however, only in 1c was there an observed microsecond component.Complex 1d, bearing the Dppe P^P ligand, showed a modestly reduced Φ PL of 1.2% and shorter bi-exponential decay (31 ns and 497 ns).6]30 In an effort to improve the Φ PL of these complexes, we evaluated the family of mesppy-containing complexes (2a, 2b, 2c).Unfortunately only a slight improvement in the solution-state photophysical properties was observed.For instance, the Φ PL for complex 2c, [Ir( ppymes) 2 (dppe)]PF 6 , was 4.5% vs. 4.2% obtained for 1c, [Ir( ppy) 2 (dppe)]PF 6 .Consistent with the energy gap law, along with the expected blue-shift in the solution-state emission (e.g., 3c: λ em = 471 nm; 1c: λ em = 488 nm) upon fluorine incorporation onto the C^N ligands, there is an observed enhanced photoluminescence quantum yield and longer emission lifetimes (e.g., 3c: 18%; 1c: 4.2%).19a,b Considering the improved photophysical properties observed for 3c, we decided to evaluate the family of dFmesppy cyclometalated complexes bearing xantphos, dpephos and dppe as ancillary ligands, with a view to reducing the intramolecular interactions and therefore the quenching phenomena following introduction of the bulky mesityl substituent. 22isappointingly, the observed Φ PL and τ e values for 4a and 4b remained essentially unaltered compared to analogs 2a and 2b.We were however delighted to observe the much-enhanced Φ PL for 4c at 52% and emission dominated by a component of lifetime of 13.5 μs compared to analog 3c.
To discern if the effects observed in MeCN solution are transposable to the solid state, dip-coated neat films were analyzed.Generally, the trends observed in solution are mirrored in the films (Table 1), with slight enhancement in Φ PL .It is worth noting that a remarkable improvement of the Φ PL in the solid state was observed for 4a and 4b, which contain the dFmesppy C^N ligands.These two complexes are nearly nonemissive in MeCN (Φ PL : 0.7% and 0.9%, respectively) with very short emission lifetimes (τ e : ca.36 ns and 89 ns, respectively) but significantly brighter in the solid state (Φ PL : 5.7% and 7.4%, respectively and τ e : ca.882 ns and 1070 ns, respectively).Thus, the non-radiative pathways in solution that result from the flexibility of the eight-membered chelate of the P^P ligand are significantly mitigated as the complexes are rigidified in the solid state.
For 1b, 1c and 1d bearing, respectively, dpephos, dppe and Dppe P^P ligands, a red shift in the emission energy (by up to 4.5 × 10 2 cm −1 ) and broader emission are observed going from solution to the solid state (Fig. S77 †).This is in agreement with many reports on aggregation phenomena of iridium(III) complexes in the solid state, in which either or both a red-shift in the emission and broadness in the emission bands is observed. 31In order to overcome such effects, the ligands are often modified to incorporate bulky groups.21i,31,32 Our results show that for 2b, 4b, 2c and 4c the bulky mesityl substituent suppresses aggregation in the solid state, with their thin film emission profiles mirroring those observed in MeCN solution.A similar, but less pronounced effect, is observed for complexes 1a and 1f, where the red-shifted emission in the solid state is noticeably reduced due to the bulkiness of the xantphos and isopropxantphos P^P ligands, respectively.

Electrochemical properties
The electrochemical properties of the complexes have been investigated by cyclic voltammetry in degassed MeCN and the oxidation potentials, E pa (V), reported with respect to SCE (Fc/ Fc + = 0.38 V in MeCN) 33 are compiled in Table S1.† For complexes bearing ppy and mesppy C^N ligands a single irreversible oxidation wave around 1.4 V is observed.When the complexes possess dFppy or dFmesppy C^N ligands, the oxidation potentials are more positive (E pa : ca.1.7 V) due to stabilization of the HOMO promoted by the fluorine electronwithdrawing substituents.Similar to other cationic iridium(III) complexes, these oxidation processes are assigned to the Ir III / Ir IV redox couple with significant involvement of the C^N ligands. 11,14The absence of an observable reduction process within the solvent window points to a large electrochemical gap promoted by the strongly σ-donating P^P ligands.

Electroluminescent devices: light-emitting electrochemical cells (LEECs)
In view of the promising thin film photoluminescence properties of some of the ionic transition metal complexes (iTMC) in this study, light-emitting electrochemical cells (LEECs) based on compounds 1b, 4a, 4b and 4c were prepared, according to the procedure described in the Experimental section.LEECs consisted of a 100 nm thick emitting layer, sandwiched between an ITO/PEDOT:PSS (80 nm) anode (ITO = indium tin oxide; PEDOT:PSS = poly(3,4-ethylenedioxythiophene) polystyrene sulfonate) and a thermally evaporated aluminum cathode (70 nm) (Fig. 5c).The PEDOT:PSS layer was used to smoothen the ITO surface and hence to increase the yield and reproducibility of working devices.The device lifetime was measured by applying a pulsed current and by monitoring the voltage and luminance versus time, with a True Colour Sensor MAZeT (MTCSiCT Sensor) and a Botest OLT OLED Lifetime-Test System.The LEECs were driven using a pulsed current of 765 A m −2 , which is a high current density for this type of devices that leads to rapid degradation.The high current density, however, was necessary to increase the light emission to a level sufficient to be detectable by our equipment.All four LEECs showed a fast voltage drop at the initial operation stage, a consequence of fast ionic motion towards the electrode interfaces, which decreases the injection barrier for electrons and holes (see Fig. S99-102 †). 34Following the electrical double layers formation at the electrode interface, the injected charges create p-and n-doped regions in the active layer close to the correspondent electrode. 35In spite of the typical electronic behavior of the LEECs, the luminance detected was rather low for all four devices.Assuming that electrons and holes are effectively injected into the active layer, the poor performance for the LEECs is attributed to the irreversibility of the phosphine ligand oxidation and to the high driving current density.
In a first attempt to exploit the potential of these new complexes, in view of their high photoluminescence efficiency, a host-guest LEEC was prepared using complex 4c in the configuration as previously described, 36 which consisted on an ionic carbazole (NMS25) and a spirobifluorene (SPPO13) as hole and electron transport materials, respectively.The hostguest layer was prepared using a NMS25 : SPPO13 mixture (1 : 1 mass ratio) doped with 10 wt% of 4c.The host-guest device showed electroluminescence at a lower current density compared to the devices employing solely the iTMC (Fig. 5a).This is an indication of a better electronic transport through the host materials compared to the pure iTMC.The absolute electroluminescence of the host-guest system is somewhat low, which could be most likely due to an inadequate alignment of the lowest unoccupied molecular orbital (LUMO) of the iTMC with respect to the LUMO of the SPPO13 (−2.9 eV), 37 resulting in inefficient energy transfer from the host (SPPO13) to the guest (4c).The reduction wave in 4c was found to lie outside the electrochemical window of the solvent (see electrochemistry section), which means that the LUMO energy of this material should be less than −2.8 eV (Fc/Fc + reference).The host-guest LEEC showed a sky-blue electroluminescence, where the maximum emission corresponds to 479 nm (Fig. 5b).
We are currently working on the preparation of more suitable polar electron transport materials to attempt to improve these host guest devices.
The electroluminescence (EL) spectra are very similar to the PL spectra of the neat films as shown in Fig. 6a, an indication that in both cases the complexes are emitting from the same excited state.Fig. 6b shows the current-voltage-luminance characteristics of two devices.The turn-on voltages for both devices are similar.Fig. 6c shows the external quantum efficiency of the devices together with the power efficiency.Both the devices exhibit similar CIE coordinates (0.20, 0.29).Despite 4c exhibiting a higher thin film Φ PL compared to 3c both OLED devices show similar poor efficiencies, which suggest that the performance of device 1 can be optimized further by improving the charge balance.

Conclusions
In summary, thirteen blue to blue-green emitting (λ em 477-510 nm) cationic heteroleptic iridium(III) complexes bearing bisphosphine ancillary ligands have been synthesized and their optoelectronic properties investigated.Through optimization of the bite angle of the P^P chelate and introduction of bulky and fluorinated C^N ligands, we have rationally designed the brightest reported blue-emitting (λ em : 471 nm) complex of this class in 4c (Φ PL : 52%).However, these complexes exhibit irreversible electrochemistry, which perhaps accounts for the poor LEEC performances observed using complexes 1b, 4a, 4b and 4c.The EL study shows that further refinement in charge balance is necessary in order to improve the performance of the OLED devices.

General synthetic procedures
Commercial chemicals were used as supplied.All reactions were performed using standard Schlenk techniques under inert (N 2 ) atmosphere with reagent grade solvents.Flash column chromatography was performed using silica gel (Silia-P from Silicycle, 60 Å, 40-63 μm).Analytical thin layer chromatography (TLC) was performed with silica plates with aluminum backings (250 μm with indicator F-254).Compounds were visualized under UV light. 1 H, 13 C, 31 P NMR 19 F NMR spectra were recorded on a Bruker Avance spectrometer at 500 MHz, 126 MHz and 471 MHz respectively.The following abbreviations have been used for multiplicity assignments: "s" for singlet, "d" for doublet, "t" for triplet, "m" for multiplet and "br" for broad.Deuterated chloroform (CDCl 3 ) and deuterated dichloromethane (CD 2 Cl 2 ) were used as the solvents of record.Melting points (Mp's) were recorded using open-ended capillaries on an Electrothermal melting point apparatus and are uncorrected.High-resolution mass spectra were recorded at the EPSRC UK National Mass Spectrometry Facility at Swansea University on a quadrupole time-of-flight (ESI-Q-TOF), model ABSciex 5600 Triple TOF in positive electrospray ionization mode and spectra were recorded using sodium formate solution as the calibrant.
Tetrakis  purging cycles and the mixture and the mixture was heated to 55 °C for 19 h under nitrogen atmosphere.The solution was cooled to room temperature and solid NH 4 PF 6 (10.0 equiv.) was added and the reaction mixture was left to stir for a further 1 h.The resulting suspension was evaporated to dryness, with the residue then copiously washed with Et 2 O and distilled water.This crude product was purified by flash column chromatography (silica, DCM/MeOH gradient 100 : 0 to 90 : 10).Fractions containing the desired complex were combined and solid NH 4 PF 6 (10 equiv.) was added.The suspension was stirred at room temperature for 0.5 h.This mixture was then evaporated to dryness, washed vigorously with distilled water and dried to afford the pure material.accumulating area detector images spanning at least a hemisphere of reciprocal space.All data were corrected for Lorentz polarization effects, and a multiscan absorption correction was applied by using CrystalClear. 38Structures were solved by Patterson methods (PATTY) 39 and refined by full-matrix leastsquares against F 2 (SHELXL-2013). 40Non-hydrogen atoms were refined anisotropically, and hydrogen atoms were refined using a riding model, except for the NH hydrogen in 1e, which was located from the difference Fourier map and refined subject to a distance restraint.All calculations were performed using the CrystalStructure interface. 41

Photophysical measurements
All samples were prepared in HPLC grade acetonitrile with varying concentrations in the order of μM.Absorption spectra were recorded at room temperature using a Shimadzu UV-1800 double beam spectrophotometer.Molar absorptivity determination was verified by linear least-squares fit of values obtained from at least four independent solutions at varying concentrations with absorbance ranging from 6.05 × 10 −5 to 2.07 × 10 −5 M. The sample solutions for the emission spectra were prepared in HPLC grade MeCN and degassed via three freezepump-thaw cycles using an in-house designed quartz cuvette.Steady state emission and excitation spectra and time-resolved emission spectra were recorded at 298 K using an Edinburgh Instruments F980.All samples for steady state measurements were excited at 360 nm while samples for time-resolved measurements were excited at 378 nm using a PDL 800-D pulsed diode laser.Emission quantum yields were determined using the optically dilute method. 32A stock solution with absorbance of ca.0.5 was prepared and then four dilutions were prepared with dilution factors between 2 and 20 to obtain solutions with absorbances of ca.0.095, 0.065, 0.05 and 0.018, respectively.The Beer-Lambert law was found to be linear at the concentrations of the solutions.The emission spectra were then measured after the solutions were rigorously degassed via three freeze-pump-thaw cycles prior to spectrum acquisition.For each sample, linearity between absorption and emission intensity was verified through linear regression analysis and additional measurements were acquired until the Pearson regression factor (R 2 ) for the linear fit of the data set surpassed 0.9.Individual relative quantum yield values were calculated for each solution and the values reported represent the slope value.The equation Φ s = Φ r (A r /A s )(I s /I r )(n s /n r ) 2 was used to calculate the relative quantum yield of each of the sample, where Φ r is the absolute quantum yield of the reference, n is the refractive index of the solvent, A is the absorbance at the excitation wavelength, and I is the integrated area under the corrected emission curve.The subscripts s and r refer to the sample and reference, respectively.A solution of quinine sulfate in 0.5 M H 2 SO 4 (Φ r = 54.6%) was used as the external reference. 29,42ectrochemistry measurements Cyclic voltammetry (CV) measurements were performed on an Electrochemical Analyzer potentiostat model 600D from CH Instruments.Solutions for cyclic voltammetry were prepared in MeCN and degassed with MeCN-saturated nitrogen by bubbling for about 10 min prior to scanning.Tetra(n-butyl)ammoniumhexafluorophosphate (TBAPF 6 ; ca.0.1 M in MeCN) was used as the supporting electrolyte.An Ag/Ag + electrode (silver wire in a solution of 0.1 M KCl in H 2 O) was used as the pseudoreference electrode; a Pt electrode was used for the working electrode and a Pt electrode was used as the counter electrode.The redox potentials are reported relative to a saturated calomel electrode (SCE) electrode with a ferrocene/ferrocenium (Fc/Fc + ) redox couple as an internal reference (0.38 V vs. SCE). 33

Electroluminescent devices
All commercial materials were used as received: aqueous dispersion of poly (3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS, CLEVIOS™ P VP Al 4083; Heraeus); ionic liquid (IL) 1-butyl-3-methyl-imidazolium tetrafluoroborate [Bmim][PF 6 ] (Aldrich) and SPPO13 (Luminescence Technology Corp.).NS25 was synthetized according to the previously reported procedure. 36The LEEC devices were made as follows.Indium tin oxide ITO-coated glass plates were patterned by conventional photolithography (Naranjo Substrates).The substrates were cleaned ultrasonically in water-soap, water and 2-propanol baths.After drying, the substrates were placed in a UV-ozone cleaner (Jelight 42-220) for 20 min.An 80 nm layer of PEDOT:PSS was spin-coated on the ITO-glass substrate.To prepare the emitting layer, the devices were spin-coated at 1000 rpm for 30 s from a solution containing either the ionic transition metal complex (iTMC) and the IL at a 4 : 1 molar ratio (iTMC : IL) or a 1 : 1 mass ratio mixture of NMS25 : SPPO13 (with 10 wt% of 4c).After deposition of the emitting layer, the devices were transferred into an inert atmosphere glovebox, where the aluminium electrode was thermally evaporated using a shadow mask.The size of the LEEC was 6.5 mm 2 .
The thickness of the films was determined with an Ambios XP-1 profilometer.Time dependence of luminance and voltage was measured by applying pulsed current and by monitoring the voltage and the luminance simultaneously by a True Colour Sensor MAZeT (MTCSICT Sensor) using a Lifetime Test System designed by BoTEST (Botest OLT OLED Lifetime-Test System).Electroluminescence spectra were recorded with an Avantes fiber-optics photo-spectrometer.
For OLED devices, ITO-coated soda lime glass substrates were cleaned by ultrasound in acetone and 2-propanol, fol-lowed by an oxygen plasma treatment.A 40 nm thick poly (3,4ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) was spin-coated on the ITO and baked on a hot plate at 120 °C for 10 min.A hole-transport layer of 35 nm-thick poly(N-vinylcarbazole) (PVK) was spin-coated on the PEDOT:PSS layer and baked at 80 °C for 2 hours in a nitrogen glove box.An emissive layer of complexes blended with 1,3-bis(N-carbazolyl)benzene (mCP) and 4-diphenylphosphoryl dibenzofuran (o-DBFPPO) were spin-coated on top of the PVK layer.An electron-transport layer of 60 nm-thick bis-4,6-(3,5-di-3-pyridylphenyl)-2-methylpyrimidine (B3PyMPM) was deposited through a shadow mask.A cathode of Ca/Al (20 nm/200 nm) was then deposited on the B3PyMPM layer in the same vacuum system.After the evaporation, the devices were encapsulated with optical curing adhesive (Norland NOA68) and glass coverslips in the glove box.The device has an active area of 2 × 1.5 mm 2 .The current-voltage-light output characteristics were measured using a Keithley source measure unit with a calibrated silicon photodiode.The EL spectra were measured using a charge coupled device spectrograph.
The syntheses of the C^N ligands and the heteroleptic iridium complexes are shown in Scheme 1.Each of dFppy, mesppy and dFmesppy were prepared in high yield via Suzuki-Miyaura 24 palladium-catalysed cross-coupling reactions.The C^N ligands were complexed with IrCl 3 •3H 2 O and the resulting the μ-dichloro-bridged iridium dimers [Ir-( ppy) 2 Cl] 2 , D1; [Ir(dFppy) 2 Cl] 2 , D2; [Ir(mesppy) 2 Cl] 2 , D3; and Eli Zysman-Colman Eli Zysman-Colman obtained his Ph.D. from McGill University in 2003 under the supervision of Prof. David N. Harpp as an FCAR scholar where he conducting research in physical organic sulfur chemistry.He then completed two postdoctoral fellowships, one in supramolecular chemistry with Jay Siegel at the Organic Chemistry Institute, University of Zurich as an FQRNT fellow and the other in inorganic materials chemistry with Stefan Bernhard at Princeton University as a PCCM fellow.He joined the department of chemistry at the Université de Sherbrooke in Quebec, Canada as an assistant professor in 2007.In 2013, he moved to the University of St Andrews where he is an EaStCHEM Research Fellow/Lecturer (tenured).His research program focuses on the rational design of: (I) luminophores for energy-efficient visual displays and flat panel lighting based on organic light emitting diode (OLED) and light-emitting electrochemical cell (LEEC) device architectures; (II) light harvesting dyes for dye-sensitized solar cells (DSSCs) and organic photovoltaics; (III) sensing materials employed in electrochemiluminescence; and (IV) photoredox catalysts for organic reactions.
3c and 4c (with dppe) the P-Ir-P bond angles are reduced to less than 90°[angles varying between 83.06(3)°and 84.49(4)°].This appears to arise from the size of the chelate formed by the P^P ligand, and its flexibility.In each of 1a, 2a, 4a, 1b, 4b and 1e an eight-membered chelate exists whereas in 1c, 3c and 4c a more rigid five membered chelate is present.Additionally, the complexes with an eight-membered chelate break down into two sub-groups depending on the flexibility of the backbone of the P^P ligand, those complexes of xantphos and nixantphos showing a range of P-Ir-P bond-angles [100.81(8)-102.53(7)°]slightly above those seen in the more conformationally flexible dpephos complexes [98.74(7)-99.53(12)°].To accommodate the varying sizes of chelate rings, the Ir-P bonds are found to vary in consequence, the complexes with smaller chelate rings showing shorter Ir-P bonds [2.3642(8)-2.3687(5)Å] than those in the complexes with larger chelate rings [2.448(4)-2.537(2)Å].

Fig. 6
Fig. 6 (a) Normalized electroluminescent emission spectra of 4c (black) and 3c (red) in thin films.Inset shows the photograph of the working OLED with 4c.(b) Current density and luminance versus applied voltage for OLEDs made with 4c (black) and 3c (red).(c) External quantum efficiency and Power efficiency versus applied voltage for OLEDs made with 4c (black) and 3c (red).(d) Schematic representation of the OLED architectures.