Highly efficient, near-infrared electrophosphorescence from a Pt-metalloporphyrin complex.
Explore the source record for details and available documents.
Journal Article↗
Biomedical subjects
Mark E Thompson
Publications and source records attributed to Mark E Thompson.
Cyclometalated iridium(III)-sensitized titanium dioxide solar cells.
Ir(III) dyes used as sensitizers in dye-sensitized solar cells produced quantum yields approaching unity for conversion of absorbed photons to current under simulated air mass 1.0 sunlight, with current production resulting from ligand-to-ligand charge-transfer states, rather than the typical metal-to-ligand charge-transfer states in ruthenium-based cells.
Journal Article↗
Enhanced open-circuit voltage in subphthalocyanine/C60 organic photovoltaic cells.
A double-heterostructure boron subphthalocyanine chloride (SubPc)/C60 thin-film photovoltaic cell exhibits a more than doubled Voc compared to a conventional copper phthalocyanine (CuPc)/C60 cell under 1 sun AM1.5G simulated illumination. The lower oxidation potential of SubPc results in an increase in the energy difference between the lowest unoccupied molecular orbital of the acceptor-like material and the highest occupied molecular orbital of the donor-like material (referred to as the interface gap, Ig) by 400 meV. We attribute the significant increase in Voc to this increase in Ig.
Journal Article↗
Management of singlet and triplet excitons for efficient white organic light-emitting devices.
Lighting accounts for approximately 22 per cent of the electricity consumed in buildings in the United States, with 40 per cent of that amount consumed by inefficient (approximately 15 lm W(-1)) incandescent lamps. This has generated increased interest in the use of white electroluminescent organic light-emitting devices, owing to their potential for significantly improved efficiency over incandescent sources combined with low-cost, high-throughput manufacturability. The most impressive characteristics of such devices reported to date have been achieved in all-phosphor-doped devices, which have the potential for 100 per cent internal quantum efficiency: the phosphorescent molecules harness the triplet excitons that constitute three-quarters of the bound electron-hole pairs that form during charge injection, and which (unlike the remaining singlet excitons) would otherwise recombine non-radiatively. Here we introduce a different device concept that exploits a blue fluorescent molecule in exchange for a phosphorescent dopant, in combination with green and red phosphor dopants, to yield high power efficiency and stable colour balance, while maintaining the potential for unity internal quantum efficiency. Two distinct modes of energy transfer within this device serve to channel nearly all of the triplet energy to the phosphorescent dopants, retaining the singlet energy exclusively on the blue fluorescent dopant. Additionally, eliminating the exchange energy loss to the blue fluorophore allows for roughly 20 per cent increased power efficiency compared to a fully phosphorescent device. Our device challenges incandescent sources by exhibiting total external quantum and power efficiencies that peak at 18.7 +/- 0.5 per cent and 37.6 +/- 0.6 lm W(-1), respectively, decreasing to 18.4 +/- 0.5 per cent and 23.8 +/- 0.5 lm W(-1) at a high luminance of 500 cd m(-2).
Journal Article↗
Whole-cell sensing for a harmful bloom-forming microscopic alga by measuring antibody--antigen forces.
Aureococcus anophagefferens, a harmful bloom-forming alga responsible for brown tides in estuaries of the Middle Atlantic U.S., has been investigated by atomic force microscopy for the first time, using probes functionalized with a monoclonal antibody specific for the alga. The rupture force between a single monoclonal antibody and the surface of A. anophagefferens was experimentally found to be 246 +/- 11 pN at the load rate of 12 nN/s. Force histograms for A. anophagefferens and other similarly-sized algae are presented and analyzed. The results illustrate the effects of load rates, and demonstrate that force-distance measurements can be used to build biosensors with high signal-to-noise ratios for A. anophagefferens. The methods described in this paper can be used, in principle, to construct sensors with single-cell resolution for arbitrary cells for which monoclonal antibodies are available.
Antigen-Antibody Complex↗
Cationic bis-cyclometalated iridium(III) diimine complexes and their use in efficient blue, green, and red electroluminescent devices.
A series of cationic Ir(III) complexes with the general formula (C/N)2Ir(N/N)(+)PF6- featuring bis-cyclometalated 1-phenylpyrazolyl-N,C2' (C/N) and neutral diimine (N/N, e.g., 2,2'-bipyridyl) ligands were synthesized and their electrochemical, photophysical, and electroluminescent properties studied. Density functional theory calculations indicate that the highest occupied molecular orbital of the compounds is comprised of a mixture of Ir d and phenylpyrazolyl-based orbitals, while the lowest unoccupied molecular orbital has predominantly diimine character. The oxidation and reduction potentials of the complexes can be independently varied by systematic modification of either the C/N or N/N ligands with donor or acceptor substituents. The electrochemical redox gaps (E(ox)-E(red)) were adjusted to span a range between 2.39 and 3.08 V. All of the compounds have intense absorption bands in the UV region assigned to 1(pi-pi*) transitions and weaker charge-transfer (CT) transitions that extend to the visible region. The complexes display intense luminescence both in fluid solution and as neat solids at 298 K that is assigned to emission from a triplet metal-ligand-to-ligand CT (3MLLCT) excited state. The energy of the 3MLLCT state varies in nearly direct proportion to the size of the electrochemical redox gap, which leads to emission colors that vary from red to blue. Three of the (C/N)2Ir(N/N)(+)PF6- complexes were used as active materials in single-layer light-emitting electrochemical cells (LECs). Single-layer electroluminescent devices were fabricated by spin-coating the Ir complexes onto an ITO-PEDOT/PSS substrate followed by deposition of aluminum contacts onto the organic film. Devices were prepared that give blue, green, and red electroluminescence spectra (lambda(max) = 492, 542, and 635 nm, respectively), which are nearly identical with the photoluminescence spectra of thin films of the same materials. The single-layer LECs give peak external quantum efficiencies of 4.7, 6.9, and 7.4% for the blue, green, and red emissive devices, respectively.
Journal Article↗
Blue and near-UV phosphorescence from iridium complexes with cyclometalated pyrazolyl or N-heterocyclic carbene ligands.
Two approaches are reported to achieve efficient blue to near-UV emission from triscyclometalated iridium(III) materials related to the previously reported complex, fac-Ir(ppz)(3) (ppz = 1-phenylpyrazolyl-N,C(2)'). The first involves replacement of the phenyl group of the ppz ligand with a 9,9-dimethyl-2-fluorenyl group, i.e., fac-tris(1-[(9,9-dimethyl-2-fluorenyl)]pyrazolyl-N,C(2)')iridium(III), abbreviated as fac-Ir(flz)(3). Crystallographic analysis reveals that both fac-Ir(flz)(3) and fac-Ir(ppz)(3) have a similar coordination environment around the Ir center. The absorption and emission spectra of fac-Ir(flz)(3) are red shifted from those of fac-Ir(ppz)(3). The fac-Ir(flz)(3) complex gives blue photoluminescence (PL) with a high efficiency (lambda(max) = 480 nm, phi(PL) = 0.38) at room temperature. The lifetime and quantum efficiency were used to determine the radiative and nonradiative rates (1.0 x 10(4) and 2.0 x 10(4) s(-1), respectively). The second approach utilizes N-heterocyclic carbene (NHC) ligands to form triscyclometalated Ir complexes. Complexes with two different NHC ligands, i.e., iridium tris(1-phenyl-3-methylimidazolin-2-ylidene-C,C(2)'), abbreviated as Ir(pmi)(3), and iridium tris(1-phenyl-3-methylbenzimidazolin-2-ylidene-C,C(2)'), abbreviated as Ir(pmb)(3), were both isolated as facial and meridianal isomers. Comparison of the crystallographic structures of the fac- and mer-isomers of Ir(pmb)(3) with the corresponding Ir(ppz)(3) isomers indicates that the imidazolyl-carbene ligand has a stronger trans influence than pyrazolyl and, thus, imparts a greater ligand field strength. Both fac-Ir(pmi)(3) and fac-Ir(pmb)(3) complexes display strong metal-to-ligand-charge-transfer absorption transitions in the UV (lambda = 270-350 nm) and phosphoresce in the near-UV region (E(0)(-)(0) = 380 nm) at room temperature with phi(PL) values of 0.02 and 0.04, respectively. The radiative decay rates for fac-Ir(pmi)(3) and fac-Ir(pmb)(3) (5 x 10(4) s(-1) and 18 x 10(4) s(-1), respectively) are somewhat higher than that of fac-Ir(flz)(3), but the nonradiative rates are two orders of magnitude faster (i.e., (2-4) x 10(6) s(-1)).
Journal Article↗
Complementary detection of prostate-specific antigen using In2O3 nanowires and carbon nanotubes.
We report complementary detection of prostate-specific antigen (PSA) using n-type In2O3 nanowires and p-type carbon nanotubes. Our innovation involves developing an approach to covalently attach antibodies to In2O3 NW surfaces via the onsite surface synthesis of phosphonic acid-succinylimide ester. Electronic measurements under dry conditions revealed complementary response for In2O3 NW and SWNT devices after the binding of PSA. Real-time detection in solution has also been demonstrated for PSA down to 5 ng/mL, a benchmark concentration significant for clinical diagnosis of prostate cancer, which is the most frequently diagnosed cancer.
Indium↗
Selective functionalization of In2O3 nanowire mat devices for biosensing applications.
A strategy to covalently attach biological molecules to the electrochemically active surface of indium oxide nanowire (In2O3 NW) mat devices is presented. A self-assembled monolayer (SAM) of 4-(1,4-dihydroxybenzene)butyl phosphonic acid (HQ-PA) was generated on an indium tin oxide (ITO)-coated glass and In2O3 NWs surface. The chemical steps required for surface derivatization were optimized on an ITO surface prior to modifying the In2O3 NWs. The hydroquinone group contained in the HQ-PA SAM was electrochemically oxidized to quinone (Q-PA) at +330 mV. The monolayer of Q-PA was allowed to react with a thiol-terminated DNA. The DNA was paired to its complementary strand tagged with a fluorescence dye. Attachment of DNA was verified using fluorescence microscopy. A device was subsequently prepared on a SiO2-supported mat of In2O3 NWs by depositing gold electrodes on the mat surface. The reaction strategy optimized on ITO was applied to this In2O3 NW-based device. Arrays of In2O3 NWs on a single substrate were electrochemically activated in a selective manner to Q-PA. Activated In2O3 NWs underwent reaction with HS-DNA and gave a positive fluorescence response after pairing with the dye-DNA. The unactivated In2O3 NWs gave no response, thus demonstrating selective functionalization of an In2O3 NW array. This can be considered a key step for the future fabrication of large-scale, inexpensive, nanoscale biosensors.
Biosensing Techniques↗
Synthetic control of excited-state properties in cyclometalated Ir(III) complexes using ancillary ligands.
The synthesis and photophysical characterization of a series of (N,C(2')-(2-para-tolylpyridyl))2 Ir(LL') [(tpy)2 Ir(LL')] (LL' = 2,4-pentanedionato (acac), bis(pyrazolyl)borate ligands and their analogues, diphosphine chelates and tert-butylisocyanide (CN-t-Bu)) are reported. A smaller series of [(dfppy)2 Ir(LL')] (dfppy = N,C(2')-2-(4',6'-difluorophenyl)pyridyl) complexes were also examined along with two previously reported compounds, (ppy)2 Ir(CN)2- and (ppy)2 Ir(NCS)2- (ppy = N,C(2')-2-phenylpyridyl). The (tpy)2 Ir(PPh2CH2)2 BPh2 and [(tpy)2 Ir(CN-t-Bu)2](CF3SO3) complexes have been structurally characterized by X-ray crystallography. The Ir-C(aryl) bond lengths in (tpy)2 Ir(CN-t-Bu)2+ (2.047(5) and 2.072(5) A) and (tpy)2 Ir(PPh2CH2)2 BPh2 (2.047(9) and 2.057(9) A) are longer than their counterparts in (tpy)2 Ir(acac) (1.982(6) and 1.985(7) A). Density functional theory calculations carried out on (ppy)2 Ir(CN-Me)2+ show that the highest occupied molecular orbital (HOMO) consists of a mixture of phenyl-pi and Ir-d orbitals, while the lowest unoccupied molecular orbital is localized primarily on the pyridyl-pi orbitals. Electrochemical analysis of the (tpy)2 Ir(LL') complexes shows that the reduction potentials are largely unaffected by variation in the ancillary ligand, whereas the oxidation potentials vary over a much wider range (as much as 400 mV between two different LL' ligands). Spectroscopic analysis of the cyclometalated Ir complexes reveals that the lowest energy excited state (T1) is a triplet ligand-centered state (3LC) on the cyclometalating ligand admixed with 1MLCT (MLCT = metal-to-ligand charge-transfer) character. The different ancillary ligands alter the 1MLCT state energy mainly by changing the HOMO energy. Destabilization of the 1MLCT state results in less 1MLCT character mixed into the T1 state, which in turn leads to an increase in the emission energy. The increase in emission energy leads to a linear decrease in ln(k(nr)) (k(nr) = nonradiative decay rate). Decreased 1MLCT character in the T1 state also increases the Huang-Rhys factors in the emission spectra, decreases the extinction coefficient of the T1 transition, and consequently decreases the radiative decay rates (k(r)). Overall, the luminescence quantum yields decline with increasing emission energies. A linear dependence of the radiative decay rate (k(r)) or extinction coefficient (epsilon) on (1/deltaE)2 has been demonstrated, where deltaE is the energy difference between the 1MLCT and 3LC transitions. A value of 200 cm(-1) for the spin-orbital coupling matrix element 3LC absolute value(H(SO)) 1MLCT of the (tpy)2 Ir(LL') complexes can be deduced from this linear relationship. The (fppy)2 Ir(LL') complexes with corresponding ancillary ligands display similar trends in excited-state properties.
Journal Article↗
Synthetic control of Pt...Pt separation and photophysics of binuclear platinum complexes.
A new series of luminescent mu-pyrazolate-bridged cyclometalated platinum binuclear complexes having the formula CwedgeNPt(mu-pz')2PtCwedgeN (CwedgeN = 2-(2,4-difluorophenyl)pyridyl, pz' = pyrazolate for 1, 3,5-dimethylpyrazolate for 2, 3-methyl-5-tert-butylpyrazolate for 3, and 3,5-bis(tert-butyl)pyrazolate for 4) have been synthesized and characterized. The two Pt(CwedgeN) moieties are bridged by two mu-pyrazolate ligands in an exo-bidentate fashion. A mononuclear complex with an isolated Pt center, CwedgeNPt(pz)2BEt2, 5, is also described. The X-ray crystal structures of 1-4 show the following Pt-Pt spacings: 1 = 3.3763(7) A, 2 = 3.1914(9) A, 3 = 3.0457(7) A, and 4 = 2.8343(6) A. At 77 K, the emission energy of the complexes varies from blue (for 1, 2, and 5) to green (for 3) to red (for 4). The changes in the photophysical properties of the binuclear complexes can be correlated with the decreasing Pt-Pt distance; the emissive state changes from a mixed ligand center triplet/metal-to-ligand charge transfer excited state (for 1 and 2) to a lower-energy, Pt-Pt metal-metal-to-ligand charge transfer state (for 3 and 4).
Journal Article↗
Fabrication of polystyrene latex nanostructures by nanomanipulation and thermal processing.
The capability to fabricate nanoscale structures is a fundamental step toward realizing the promise and potential of nanotechnology. We report on precise manipulation and thermal processing using 100-nm polystyrene latex nanoparticles. This approach is illustrated by fabricating a three-dimensional nanostructure by using an AFM tip to position nanoparticles and then thermally processing to "sinter" the particles to form a contiguous, stable structure. We suggest that this is a general approach, but the use of polystyrene latex particles offers an advantage of low-temperature processing. Use of polystyrene latex also extends the range of materials for which we have demonstrated manipulation and suggests applications including fluorescent doping and electrically conducting polymers.
Crystallization↗
Platinum-functionalized random copolymers for use in solution-processible, efficient, near-white organic light-emitting diodes.
A near-white light-emitting polymer, consisting of hole transport (HT), electron transport (ET), and phosphorescent Pt functionalities, was prepared and utilized as the emissive layer in solution-processed OLEDs. The air-stable devices had a maximum external quantum efficiency of 4.6%.
Journal Article↗
Organometallic complexes as hole-transporting materials in organic light-emitting diodes.
The use of metal complexes fac-tris(1-phenylpyrazolato-N,C(2)('))cobalt(III) [fac-Co(ppz)(3)], fac-tris(2-phenylpyridinato-N,C(2)(') cobalt(III) [fac-Co(ppy)(3)], and [tris[2-((pyrrole-2-ylmethylidene)amino)ethyl]amine]gallium(III) [Ga(pma)] as materials for hole-transporting layers (HTL) in organic light-emitting diodes (OLEDs) is reported. Co(ppz)(3) and Co(ppy)(3) were prepared by following literature procedures and isolated as mixtures of facial (fac) and meridional (mer) isomers. The more stable fac isomers were separated from the unstable mer forms via column chromatography and thermal gradient sublimation. Crystals of fac-Co(ppz)(3) are monoclinic, space group P2(1)/c, with a = 13.6121(12) A, b = 15.5600(12) A, c = 22.9603(17) A, beta = 100.5 degrees, V = 4781.3(7) A(3), and Z = 8. [Tris[2-((pyrrol-2-ylmethylidene)amino)ethyl]amine]gallium [Ga(pma)] was prepared by the reaction of gallium(III) nitrate with the pmaH(3) ligand precursor in methanol. Ga(pma) crystallizes in the cubic space group I3d with cell parameters a = 20.2377(4) A, b = 20.2377(4) A, c = 20.2377(4) A, beta = 90.0 degrees, V = 8288.6(3) A(3), and Z = 16. These cobalt and gallium complexes are pale colored to colorless solids, with optical energy gaps ranging 2.6-3.36 eV. A two-layer HTL/ETL (ETL = electron-transporting layer) device structure using fac-Co(ppz)(3) and fac-Co(ppy)(3) as the HTL does not give efficient electroluminescence. However, the introduction of a thin layer of a hole-transporting material (N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine, NPD) as an energy "stair-step" and electron/exciton-blocker dramatically improves the device performance. Both fac-Co(ppz)(3) and fac-Co(ppy)(3) devices give external quantum efficiencies higher than 1.0%, with brightness 5000 and 7000 Cd/m(2) at 10 V, respectively. Ga(pma) also functions as an efficient interface layer, giving device performances very similar to those of analogous devices using NPD as the interface layer. Stability tests have been carried out for Co(ppz)(3)/NPD/Alq(3) and Co(ppy)(3)/NPD/Alq(3) devices. While fac-Co(ppy)(3) gave stable OLEDs, the fac-Co(ppz)(3)-based devices had very short lifetimes. On the basis of the experimental results of chemical oxidation of fac-Co(ppz)(3), the major cause for the fast decay of the fac-Co(ppz)(3) device is proposed to be the decomposition of fac-Co(ppz)(3)(+) in the HTL layer during the device operation.
Journal Article↗
Simultaneous light emission from a mixture of dendrimer encapsulated chromophores: a model for single-layer multichromophoric organic light-emitting diodes.
The site isolation of two dyes capable of electronic interaction via Forster energy transfer has been studied with the two dyes coumarin 343 and pentathiophene encapsulated by dendrons containing both solubilizing and electroactive moieties. Photoluminescence studies of mixtures of the dendritic dyes show that at high dendron generation, significant site isolation is achieved with relative emission characteristics influenced by both the degree of site isolation and the emission quantum yield of the dyes. Electroluminescence studies carried out in organic light emitting diode devices confirm that color tuning may be achieved by mixing the two encapsulated dyes in a single layer. However, selective carrier trapping by one of the core component dyes can dramatically influence the effectiveness of other components in the device.
Journal Article↗
Phosphorescence quenching by conjugated polymers.
Energy transfer between phosphors and conjugated polymers was investigated using a fluorene trimer (F3) as a model conjugated material. The phosphors studied were bis-cyclometalated iridium complexes (FP, PPY, BT, PQ, and BTP), with triplet energies of 2.6, 2.4, 2.2, 2.1, and 2.0 eV, respectively (based on phosphorescence spectra). Stern-Volmer analysis of luminescent quenching shows that energy transfer from either FP or PPY to F3 is an exothermic process with Stern-Volmer quenching constants (kqSV) of near 109 M-1 s-1 while energy transfer from BT, PQ, and BTP is endothermic (kqSV = 107-106 M-1 s-1). On the the basis of above results, the triplet energy of F3 is estimated to be less than 2.3 eV (530 nm). This study suggests that conjugated polymers, which typically have lower T1 energies than F3, should also quench phosphorescent emission in thin films and organic light-emitting diodes (OLEDs) incorporating these and related phosphorescent dopants.
Journal Article↗
Synthesis and characterization of facial and meridional tris-cyclometalated iridium(III) complexes.
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.
Journal Article↗
Bis-cyclometalated Ir(III) complexes as efficient singlet oxygen sensitizers.
We report the singlet oxygen sensitization properties of a series of bis-cyclometalated Ir(III) complexes (i.e., (bt)2Ir(acac), (bsn)2Ir(acac), and (pq)2Ir(acac); bt = 2-phenylbenzothiazole, bsn = 2-(1-naphthyl)benzothiazole, pq = 2-phenylquinoline, and acac = acetylacetonate). Complexes with acetylacetonate ancillary ligands give singlet oxygen quantum yields near unity (PhiDelta = (0.7-1.0) +/- 0.1), whether exciting the ligand-based state or the lowest energy excited state (MLCT + 3LC). The singlet oxygen quenching rates for these beta-diketonate complexes were found to be small [(5 +/- 2) x 105 to (6 +/- 0.2) x 106 M-1 s-1], roughly 3 orders of magnitude slower than the corresponding phosphorescence quenching rate. Similar complexes were prepared with glycine or pyridine tethered to the Ir(III) center (i.e., (bsn)2Ir(gly) and (bt)2Ir(py)Cl; gly = glycine and py = pyridine). The glycine and pyridine derivatives give high singlet oxygen yields (PhiDelta = (0.7-1.0) +/- 0.1).
Iridium↗