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PubMed2006

Ultramicroband array electrode. 1. Analysis of mercury in contaminated soils and flue gas exposed samples using a gold-plated iridium portable system by anodic stripping voltammetry.

The applicability of a gold-plated iridium Nano-Band array ultramicroelectrode (6 microm by 0.2 microm, 64-microm interspacing, 100 electrode bands) in the analysis of mercury using a portable system is demonstrated by anodic stripping voltammetry in real-life samples. Optimized measurement parameters, 0.1 M HCl electrolyte, plating potential of 0 mV, and staircase scan mode were identified. The dynamic linear range is 10-180 ppb at 5-s deposition time with 1.5 microC of gold plated. The experimental detection limit for Hg2+ in 0.1 M HCl was 0.5 ppb at a deposition time of 4 min and a scan rate of 10 V/s. Real-life samples, such as flue gas exposed samples from flue gas simulators could be analyzed within 5 min using the method of standard additions. We identified a field-portable extraction procedure for soil samples using 1:1 concentrated HNO3/30% H2O2 mixture, compatible with ASV and the iridium electrode. The detection limit for soils is 1 ppm. The results obtained using ASV are in good agreement with reference values using cold vapor atomic absorption for the sample matrixes studied here. To our knowledge, this is the first mercury application using a reusable iridium array ultramicroelectrode. The portable potentiostat is less than 500 g, and together with the portable digestion method, makes the Nano-Band Explorer system field applicable.

Electrodes↗
PubMed2003

New luminescent cyclometalated iridium(III) diimine complexes as biological labeling reagents.

We report the synthesis, characterization, and photophysical and electrochemical properties of thirty luminescent cyclometalated iridium(III) diimine complexes [Ir(N-C)(2)(N-N)](PF(6)) (HN-C = 2-phenylpyridine, Hppy; 2-(4-methylphenyl)pyridine, Hmppy; 3-methyl-1-phenylpyrazole, Hmppz; 7,8-benzoquinoline, Hbzq; 2-phenylquinoline, Hpq; N-N = 4-amino-2,2'-bipyridine, bpy-NH(2); 4-isothiocyanato-2,2'-bipyridine, bpy-ITC; 4-iodoacetamido-2,2'-bipyridine, bpy-IAA; 5-amino-1,10-phenanthroline, phen-NH(2); 5-isothiocyanato-1,10-phenanthroline, phen-ITC; 5-iodoacetamido-1,10-phenanthroline, phen-IAA). The X-ray crystal structure of [Ir(mppz)(2)(bpy-NH(2))](PF(6)) has also been investigated. Upon irradiation, all the complexes display intense and long-lived luminescence under ambient conditions and in 77-K glass. On the basis of the photophysical and electrochemical data, the emission of most of these complexes is assigned to an excited state of predominantly triplet metal-to-ligand charge-transfer ((3)MLCT) (dpi(Ir) --> pi(N-N)) character. In some cases, triplet intraligand ((3)IL) (pi --> pi)(N-N or N-C(-)) excited states have also been identified. In view of the specific reactivity of the isothiocyanate and iodoacetamide moieties toward the primary amine and sulfhydryl groups, respectively, we have labeled various biological molecules with a selection of these luminescent iridium(III) complexes. The photophysical properties of the luminescent conjugates have been investigated. In addition, a heterogeneous assay for digoxin has also been designed on the basis of the recognition of biotinylated anti-digoxin by avidin labeled with one of the luminescent iridium(III) complexes.

Crystallography, X-Ray↗
PubMed2005

Catalytic reductive alkylation of secondary amine with aldehyde and silane by an iridium compound.

[reaction: see text] An efficient methodology for the reductive alkylation of secondary amine with aldehyde and Et(3)SiH using an iridium complex as a catalyst has been developed. For example, treatment of dibutylamine with butyraldehyde and Et(3)SiH (a 1:1:1 molar amount of amine, aldehyde, and silane) in 1,4-dioxane at 75 degrees C under the influence of a catalytic amount of [IrCl(cod)](2) gave tributylamine in quantitative yield. In this reaction, no reduction of aldehyde took place. It was found that IrCl(3), which is a starting material for preparation of iridium complexes such as [IrCl(cod)](2), acts as an efficient catalyst for the present reductive alkylation of amine. In addition, a cheaper, easy-to-handle, and environmentally friendly reducing reagent such as polymethylhydrosiloxane (PMHS) in place of Et(3)SiH was also useful. Thus, a variety of secondary amines could be alkylated by allowing them to react with aldehydes and PMHS in the presence of an iridium catalyst to afford the corresponding tertiary amines in good to excellent yields. From the deuterium label experiments, it was revealed that silane and water, generated during the formation of enamine by the reaction of amine and aldehyde, seem to behave as a hydrogen source. The catalytic cycle was discussed.

Aldehydes↗
PubMed2002

Translocation of ultrafine insoluble iridium particles from lung epithelium to extrapulmonary organs is size dependent but very low.

Recently it was speculated that ultrafine particles may translocate from deposition sites in the lungs to systemic circulation. This could lead to accumulation and potentially adverse reactions in critical organs such as liver, heart, and even brain, consistent with the hypothesis that ultrafine insoluble particles may play a role in the onset of cardiovascular diseases, as growing evidence from epidemiological studies suggests. Ultrafine (192)Ir radio-labeled iridium particles (15 and 80 nm count median diameter) generated by spark discharging were inhaled by young adult, healthy, male WKY rats ventilated for 1 h via an endotracheal tube. After exposure, excreta were collected quantitatively. At time points ranging from 6 h to 7 d, rats were sacrificed, and a complete balance of (192)Ir activity retained in the body and cleared by excretion was determined gamma spectroscopically. Thoracic deposition fractions of inhaled 15- and 80-nm (192)Ir particles were 0.49 and 0.28, respectively. Both batches of ultrafine iridium particles proved to be insoluble (<1% in 7 d). During wk 1 after inhalation particles were predominantly cleared via airways into the gastrointestinal tract and feces. This cleared fraction includes particles deposited in the alveolar region. Additionally, minute particle translocation of <1% of the deposited particles into secondary organs such as liver, spleen, heart, and brain was measured after systemic uptake from the lungs. The translocated fraction of the 80-nm particles was about an order of magnitude less than that of 15-nm particles. In additional studies, the biokinetics of ultrafine particles and soluble (192)Ir was studied after administration by either gavage or intratracheal instillation or intravenous injection. They confirmed the low solubility of the particles and proved that (1) particles were neither dissolved nor absorbed from the gut, (2) systemically circulating particles were rapidly and quantitatively accumulated in the liver and spleen and retained there, and (3) soluble (192)Ir instilled in the lungs was rapidly excreted via urine with little retention in the lungs and other organs. This study indicates that only a rather small fraction of ultrafine#10; iridium particles has access from peripheral lungs to systemic circulation and extrapulmonary organs. Therefore, the hypothesis that systemic access of ultrafine insoluble particles may generally induce adverse reactions in the cardiovascular system and liver leading to the onset of cardiovascular diseases needs additional detailed and differentiated consideration.

Administration, Inhalation↗
PubMed2004

Structural analyses by TEM of iridium deposited on TiO2 powder and rutile single crystal.

It was found by transmission electron microscopy (TEM) that deposition precipitation of Ir onto TiO2 powder (Degussa P-25) produced Ir particles preferentially on the rutile phase. Iridium oxide particles supported on rutile TiO2 single crystal by deposition precipitation were also observed by TEM and scanning electron microscopy, and were found to exist as thin films of a few atoms. A structural change caused by hydrogen reduction was observed using high-resolution TEM and this was confirmed to be the iridium oxide film being reduced to metallic iridium particles.

Crystallization↗
PubMed1994

P wave recognition and atrial stimulation with fractally iridium coated VDD single pass leads.

UNLABELLED: The bottleneck of VDD systems is the reliable detection of the small atrial signals by a floating atrial electrode. Fractally iridium coated electrodes offer excellent sensing and pacing performance. In this study, the performance of such a floating atrial lead in P wave sensing and synchronous ventricular stimulation was examined. Atrial pacing was also used as a test of atrial wall contact. PATIENTS AND METHODS: A fractally iridium coated VDD lead was implanted in 18 patients. In 15 patients it was interfaced with a VDD pacemaker and in 3 patients with a DDD system depending on the P wave amplitude measured acutely (> or = 2 mV). Simultaneous recordings of the surface ECG and pacemaker telemetry were used to analyze P wave amplitudes and AV synchrony in different body positions, and during normal and deep breathing. Additionally, exercise tests based on daily life activities and 24-hour ECG monitoring were performed to test the pacemaker function. RESULTS: During implantation P wave amplitudes were 1.86 mV +/- 1.08 mV (range 0.5-4.9 mV) and during follow-up (6.6 +/- 5.6 weeks) 0.18-3.8 mV. Holter recordings revealed reliable P wave sensing at a sensitivity setting of 0.5 mV (95.5%). P wave sensing was further improved by a higher atrial sensitivity. AV synchronous pacing > or = 99.9% was achieved in all patients. In 7 patients the atrial electrode could be positioned close to the atrial wall enabling atrial stimulation thresholds at an average of 4.3 volts. CONCLUSION: This fractally iridium coated VVD lead allowed consistent and reliable P wave sensing at an atrial sensitivity as low as 0.5 mV in selected patients.

Aged↗
PubMed2000

The recording of monophasic action potentials with fractal-coated iridium electrodes in humans.

The present study was designed to evaluate the feasibility of the recording of monophasic action potentials (MAP) with fractal-coated iridium electrodes in a clinical setting. In 18 patients who underwent an electrophysiological study for various arrhythmias, we performed MAP recordings with both 1.3-mm2 and 6-mm2 tip surface area fractal-coated iridium and standard silver--silver chloride (Ag/AgCl) electrodes in the high right atrium and two ventricular positions. Amplitude and MAP duration at 90%, 50%, and 25% of repolarization were calculated during steady-state pacing at 600, 500, and 400 ms cycle lengths with extrastimuli application. Morphology comparisons of MAP signals recorded with both types of electrodes were performed by regression analysis using 5% of the repolarization segments of the MAP trajectory. Differences between MAP duration at 90%, 50%, and 25% of repolarization recorded with fractal-coated and Ag/AgCl electrodes were statistically insignificant. Amplitude values recorded with 6-mm2 tip electrodes were significantly smaller than those recorded with Ag/AgCl electrodes for all comparisons. During steady-state pacing, the correlation coefficients between Ag/AgCl and fractal-coated 1.3-mm2 and 6-mm2 tip electrodes were within the range of 0.93-0.999 and 0.87-0.999, respectively. The correlation of MAP amplitude and duration at 90%, 50%, and 25% of repolarization following the extrastimulus S2, recorded with both types of electrodes, was significantly weaker for right atrial recordings (r value range 0.78-0.92) as compared to ventricular recordings (r value range 0.92-0.99). The MAP sensing features of fractal-coated iridium and Ag/AgCl electrodes are comparable. The best results for recording of MAPs with fractal-coated electrodes can be achieved with small surface area tip electrodes.

Action Potentials↗
PubMedDate not supplied

Interstitial microwave-induced hyperthermia and iridium brachytherapy for the treatment of obstructing biliary carcinomas.

In a phase I clinical study, 10 patients with obstructive biliary carcinomas were treated with single-antenna interstitial microwave hyperthermia and iridium-192 brachytherapy. For each patient a standard biliary drainage catheter was implanted percutaneously through the obstructed common bile duct. This catheter accommodated a single microwave antenna which operated at 915 MHz, and one or two fibreoptic thermometry probes for temperature measurement. Under fluoroscopic guidance the microwave antenna and temperature probes were positioned in the CT-determined tumour mass. The 60-min heat treatment achieved a central tumour temperature of 45-55 degrees C while keeping temperatures at the proximal and distal margins at 43 degrees C. Immediately following the hyperthermia treatment the microwave antenna and temperature probes were removed, and a single strand of iridium-192 double-strength seeds was inserted to irradiate the tumour length. A dose of 5500-7900 cGy calculated at 0.5 cm radially from the catheter was administered over 5-7 days. Upon removal of the iridium a second hyperthermia treatment was performed. A total of 18 hyperthermia treatments were administered to the 10 patients. In two cases the second hyperthermia treatment after brachytherapy was not possible due to a kink in the catheter, or bile precipitation in the catheter. All patients tolerated the procedure well, and there were no acute complications. To evaluate the volumetric heating potential of this hyperthermia method, specific absorption rate (SAR) values were measured at 182 planar points in muscle phantom. Insulated and non-insulated antenna performance was tested at 915 MHz in a biliary catheter filled with air, saline, or bile to mimic clinical treatments. The insulated antenna exhibited the best performance. Differences between antenna performance in saline and bile were also noted. In summary, this technique may have potential for tumours which obstruct biliary drainage and are accessible to percutaneous decompression using standard diagnostic radiological procedures.

Biliary Tract Neoplasms↗
PubMed1999

Interstitial brachytherapy using iridium-192 for malignant brain tumors: clinical results.

OBJECTIVE: To determine the effects and toxicity of interstitial brachytherapy using iridium-192 on brain malignant gliomas. METHODS: Between January 1992 and January 1995, 56 patients with anaplastic astrocytoma and glioblastoma multiforme were treated with stereotactic brachytherapy using temporary high-activity iridium-192 sources. RESULTS: The median survival for patients receiving brachytherapy was 28 months. The survival rates at 1, 2, 3 years were 92.8%, 83.9% and 71.4% respectively. CONCLUSIONS: Brachytherapy may improve the control of local tumor and prolong the survival, when used in deep malignant brain gliomas, by temporary implanted high doses of iridium-192 sources.

Adult↗
PubMed2006

Postoperative radiotherapy with high dose rate iridium 192 mould for prevention of earlobe keloids.

BACKGROUND: A 50% to 80% recurrence rate of earlobe keloids can occur following a simple excision. Many modalities, including radiotherapy, have been suggested to reduce the postoperation recurrence. OBJECTIVE: The aim of the present study was to determine the efficacy of postoperative radiotherapy by a high dose rate Iridium 192 mould in the prevention of earlobe keloids recurrence. MATERIAL AND METHOD: Between March 1999 and March 2003, 22 patients with 24 earlobe keloids were treated by radiotherapy immediately following surgical excision. A dose of 15 Gray in 3 fractions was delivered at a point placed 5 mm from the axis of the Iridium sources. RESULTS: From the 22 patients with 24 keloids who were treated, 15 patients with 16 keloids were followed for a minimum of 6 months. Recurrence occurred in two keloids (12.5%). There were no severe adverse effects. CONCLUSION: Postoperative radiotherapy by high dose rate Iridium 192 mould was an effective prevention of earlobe keloids recurrence. It was well tolerated and did not present any significant side effects.

Adolescent↗
PubMed1986

[Side effects of postoperative irradiation of uterine cancer with high dose rate iridium and low dose rate radium].

A report is given about reversible and irreversible complications following postoperative irradiation in cases of endometrial carcinoma. Intravaginal brachytherapy was performed. In advanced cases or in cases with poor prognosis (tumor grading) percutaneous irradiation was added (Co60). In 156 cases low-dose-rate irradiation (Ra226) and in 143 cases high-dose-rate irradiation (Ir192) was applied intravaginally. Reversible complications (cystitis, proctitis) could be observed following Radium in 7%, following Iridium in 14%. Irreversible complications (fistulas, stenoses): 1.9% following Radium and 3.5% following Iridium. When high-dose-rate irradiation was combined with percutaneous Co60 therapy, reversible complications occurred in 22.8%. After changing the Iridium-therapy scheme (reduction of dose from 10 to 7 Gy and irradiation only of the upper two thirds of the vagina) complications only could be observed in the same level as in Radium-therapy. High-dose-rate irradiation does not need hospitalization of the patients.

Brachytherapy↗
PubMed1983

[Cytologic endometrial changes following high-dose iridium-192 radiation].

By intrauterine exfoliative smear performed twice in each of seventeen patients, the cytomorphologic effect of an iridium-192 after-loading irradiation was demonstrated. The examinations showed that the cytologic findings were characteristic of the effect of ionizing radiation even in case of the histologically unchanged, not radiosensitive cylindrical epithelium. After the iridium irradiation of malignantly transformed cells of the cylindrical epithelium with 1000 rd, vacuolation and pseudoeosinophilia were the predominant lesions, while after 2000 rd this was above all the presence of macronucleoli. A marked cellular diathesis is a characteristic result of the irradiation with iridium-192. Although hyperchromasia is not an absolute sign of malignancy in case of the adenocarcinoma, it should be mentioned that chromatin concentrations are scarcely found after irradiation.

Adenocarcinoma↗
PubMed2002

Large effects of ion pairing and protonic-hydridic bonding on the stereochemistry and basicity of crown-, azacrown-, and cryptand-222-potassium salts of anionic tetrahydride complexes of iridium(III).

The compounds [K(Q)][IrH(4)(PR(3))(2)] (Q = 18-crown-6, R = Ph, (i)Pr, Cy; Q = aza-18-crown-6, R = (i)Pr; Q = 1,10-diaza-18-crown-6, R = Ph, (i)Pr, Cy; Q = cryptand-222, R = (i)Pr, Cy) were formed in the reactions of IrH(5)(PR(3))(2) with KH and Q. In solution, the stereochemistry of the salts of [IrH(4)(PR(3))(2)](-) is surprisingly sensitive to the countercation: either trans as the potassium cryptand-222 salts (R = Cy, (i)Pr) or exclusively cis (R = Cy, Ph) as the crown- and azacrown-potassium salts or a mixture of cis and trans (R = (i)Pr). There is IR evidence for protonic-hydridic bonding between the NH of the aza salts and the iridium hydride in solution. In single crystals of [K(18-crown-6)][cis-IrH(4)(PR(3))(2)] (R = Ph, (i)Pr) and [K(aza-18-crown-6)][cis-IrH(4)(P(i)Pr(3))(2)], the potassium bonds to three hydrides on a face of the iridium octahedron according to X-ray diffraction studies. Significantly, [K(1,10-diaza-18-crown-6)][trans-IrH(4)(P(i)Pr(3))(2)] crystallizes in a chain structure held together by protonic-hydridic bonds. In [K(1,10-diaza-18-crown-6)][cis-IrH(4)(PPh(3))(2)], the potassium bonds to two hydrides so that one NH can form an intra-ion-pair protonic-hydridic hydrogen bond while the other forms an inter-ion-pair NH.HIr hydrogen bond to form chains through the lattice. Thus, there is a competition between the potassium and NH groups in forming bonds with the hydrides on iridium. The more basic P(i)R(3) complex has the lower N-H stretch in the IR spectrum because of stronger N[bond]H...HIr hydrogen bonding. The trans complexes have very low Ir-H wavenumbers (1670-1680) due to the trans hydride ligands. The [K(cryptand)](+) salt of [trans-IrH(4)(P(i)Pr(3))(2)](-) reacts with WH(6)(PMe(2)Ph)(3) (pK(alpha)(THF) 42) to give an equilibrium (K(eq) = 1.6) with IrH(5)(P(i)Pr(3))(2) and [WH(5)(PMe(2)Ph)(3)](-) while the same reaction of WH(6)(PMe(2)Ph)(3) with the [K(18-crown-6)](+) salt of [cis-IrH(4)(P(i)Pr(3))(2)](-) has a much larger equilibrium constant (K(eq) = 150) to give IrH(5)(P(i)Pr(3))(2) and [WH(5)(PMe(2)Ph)(3)](-); therefore, the tetrahydride anion displays an unprecedented increase (about 100-fold) in basicity with a change from [K(crypt)](+) to [K(crown)](+) countercation and a change from trans to cis stereochemistry. The acidity of the pentahydrides decrease in THF as IrH(5)(P(i)Pr(3))(2)/[K(crypt)][trans-IrH(4)(P(i)Pr(3))(2)] (pK(alpha)(THF) = 42) > IrH(5)(PCy(3))(2)/[K(crypt)][trans-IrH(4)(PCy(3))(2)] (pK(alpha)(THF) = 43) > IrH(5)(P(i)Pr(3))(2)/[K(crown)][cis-IrH(4)(P(i)Pr(3))(2)] (pK(alpha)(THF) = 44) > IrH(5)(PCy(3))(2)/[K(crown)][cis-IrH(4)(PCy(3))(2)]. The loss of PCy(3) from IrH(5)(PCy(3))(2) can result in mixed ligand complexes and H/D exchange with deuterated solvents. Reductive cleavage of P-Ph bonds is observed in some preparations of the PPh(3) complexes.

Journal Article↗
PubMed2005

Discrete iridium pyridonate chains with variable metal valence: nature and energetics of the Ir-Ir bonding from DFT calculations.

The structure of the Ir(I) complex [Ir2(mu-OPy)2(CO)4] (Opy = 2-pyridonate) has been fully characterized in its head-to-head (A) configuration as a "dimer of dimers" AA in which two binuclear complexes are connected by means of a weak, but unsupported, iridium-iridium interaction (Ir(2)...Ir(2A) 2.9808(6) A). The head-to-tail isomer, referred to as B, was found in equilibrium with A in solution. It has been shown that this complex can be oxidized by diiodine to give iridium chains with highly selective configurations and general formula I-[Ir2(mu-OPy)2(CO)4]n-I (n = 1-3). The synthesis of IAI (1), of the isomers IAAI (2AA) and IABI (2AB), and of IABAI (3) is reported. DFT calculations have been carried out on A and B and on the known isomers of 1-3, as well as on two isomers of the hypothetic chain of eight Ir(1.25) atoms corresponding to n = 4. The stability of the metal chain is assigned to a 2-electron/2n-center sigma bond delocalized along the metal backbone and supplemented with a weak attractive interaction of the metallophilic type. Calculations confirm that further oxidation of the Ir chains corresponding to n > 1 by iodine, yielding the cleavage of one or two unsupported bond(s), is a highly exothermic process. The formation of the I-[Ir2(mu-OPy)2(CO)4]n-I chains is also computed to be exothermic, either highly for n = 1 or still significantly for n = 2 and 3. At variance with these results, the formation of an octanuclear chain is predicted to be no more than marginally exothermic (DeltaG = 1.7 kcal.mol(-1)), mainly because of interligand strain induced by the steric bulk of the amidate rings.

Journal Article↗
PubMed2005

Selective cleavage of the C-C bonds of aminoethyl groups, via a multistep pathway, by a pincer iridium complex.

A pincer-ligated iridium complex is found to react with N-ethylamines, HN(Et)R (R = cyclohexyl, tert-butyl, ethyl), to give the corresponding iridium isocyanide complexes (PCP)Ir(CH3)(H)(CNR) (PCP = kappa3-2,6-(tBu2PCH2)2C6H3). This novel, regioselective C-C bond cleavage reaction occurs readily under mild conditions (25-45 degrees C). The reaction is shown to proceed via initial dehydrogenation of the amine to give the corresponding imine (N-ethylidenealkylamine). The ethylidene sp2 C-H bond then undergoes addition to iridium, followed by methyl migration.

Journal Article↗
PubMed2005

Carbon-fluorine bond activation coupled with carbon-hydrogen bond formation alpha to iridium: kinetics, mechanism, and diastereoselectivity.

Reactions of iridium(fluoroalkyl)hydride complexes CpIr(PMe(3))(CF(2)R(F))Y (R(F) = F, CF(3); Y = H, D) with LutHX (Lut = 2,6-dimethylpyridine; X = Cl, I) results in C-F activation coupled with hydride migration to give CpIr(PMe(3))(CYFR(F))X as variable mixtures of diastereomers. Solution conformations and relative diastereomer configurations of the products have been determined by (19)F{(1)H}HOESY NMR to be (S(C), S(Ir))(R(C), R(Ir)) for the kinetic diastereomer and (R(C), S(Ir))(S(C), R(Ir)) for its thermodynamic counterpart. Isotope labeling experiments using LutDCl/CpIr(PMe(3))(CF(2)R(F))H and CpIr(PMe(3))(CF(2)R(F))D/LutHCl) showed that, unlike a previously studied system, H/D exchange is faster than protonation of the alpha-CF bond, giving an identical mixture of product isotopologues from both reaction mixtures. The kinetic rate law shows a first-order dependence on the concentration of iridium substrate, but a half-order dependence on that of LutHCl; this is interpreted to mean that LutHCl dissociates to give HCl as the active protic source for C-F bond activation. Detailed kinetic studies are reported, which demonstrate that lack of complete diastereoselectivity is not a function of the C-F bond activation/H migration steps but that a cationic intermediate plays a double role in loss of diastereoselectivity; the intermediate can undergo epimerization at iridium before being trapped by halide and can also catalyze the epimerization of kinetic diastereomer product to thermodynamic product. A detailed mechanism is proposed and simulations performed to fit the kinetic data.

Journal Article↗
PubMed2005

Studies of iridium nanoparticles using density functional theory calculations.

The energetics and the electronic and magnetic properties of iridium nanoparticles in the range of 2-64 atoms were investigated using density functional theory calculations. A variety of different geometric configurations were studied, including planar, three-dimensional, nanowire, and single-walled nanotube. The binding energy per atom increases with size and dimensionality from 2.53 eV/atom for the iridium dimer to 6.09 eV/atom for the 64-atom cluster. The most stable geometry is planar until four atoms are reached and three-dimensional thereafter. The simple cubic structure is the most stable geometric building block until a strikingly large 48-atom cluster, when the most stable geometry transitions to face-centered cubic, as found in the bulk metal. The strong preference for cubic structure among small clusters demonstrates their rigidity. This result indicates that iridium nanoparticles intrinsically do not favor the coalescence process. Nanowires formed from linear atomic chains of up to 4-atom rings were studied, and the wires formed from 4-atom rings were extremely stable. Single-walled nanotubes were also studied. These nanotubes were formed by stacking 5- and 6-atom rings to form a tube. The ring stacking with each atom directly above the previous atom is more stable than if the alternate rings are rotated.

Journal Article↗
PubMed2005

Substituent effects of iridium complexes for highly efficient red OLEDs.

This study reports substituent effects of iridium complexes with 1-phenylisoquinoline ligands. The emission spectra and phosphorescence quantum yields of the complexes differ from that of tris(1-phenylisoquinolinato-C2,N)iridium(iii)(Irpiq) depending on the substituents. The maximum emission peak, quantum yield and lifetime of those complexes ranged from 598-635 nm, 0.17-0.32 and 1.07-2.34 micros, respectively. This indicates the nature of the substituents has a significant influence on the kinetics of the excited-state decay. The substituents attached to phenyl ring have an influence on a stability of the HOMO. Furthermore, those substituents have effect on the contribution to a mixing between 3pi-pi* and (3)MLCT for the lowest excited states. Some of the complexes display the larger quantum yield than Irpiq, which has the quantum yield of 0.22. The organic light emitting diode (OLED) device based on tris [1-(4-fluoro-5-methylphenyl)isoquinolinato-C2,N]iridium(iii)(Ir4F5Mpiq) yielded high external quantum efficiency of 15.5% and a power efficiency of 12.4 lm W(-1) at a luminance of 218 cd m(-2). An emission color of the device was close to an NTSC specification with CIE chromaticity characteristics of (0.66, 0.34).

Journal Article↗