Photophysical properties of highly luminescent copper(I) halide complexes chelated with 1,2-bis(diphenylphosphino)benzene

Studies on synthesis, structures, and photophysics have been carried out for a series of luminescent copper(I) halide complexes with the chelating ligand, 1,2-bis[diphenylphosphino]benzene (dppb). The complexes studied are halogen-bridged dinuclear complexes, [Cu(mu-X)dppb]2 (X = I (1), Br (2), Cl (3)), and a mononuclear complex, CuI(dppb)(PPh3) (4). These complexes in the solid state exhibit intense blue-green photoluminescence with microsecond lifetimes (emission peaks, lambdamax = 492-533 nm; quantum yields, Phi = 0.6-0.8; and lifetimes, tau = 4.0-10.4 mus) at 298 K. In 2-methyltetrahydrofuran (2mTHF) solutions at 298 K, only 1 and 4 show weaker emission (Phi = 0.009) with shorter lifetimes (tau = 0.35 and 0.23 mus) and red-shifted spectra (lambdamax = 543 and 546 nm). The emission in the solid state originates from the (M + X)LCT excited state with a distorted-tetrahedral conformation, in which emissive excited states, 1(M + X)LCT and 3(M + X)LCT, are in equilibrium with an energy difference of approximately 2 kcal/mol. On the other hand, the complexes in the 2mTHF solutions emit from the MLCT excited state with an energetically favorable flattened conformation in the temperature range of 298-130 K. The flattened geometry with equilibrated 1MLCT and 3MLCT states has a nonradiative rate at least 2 orders of magnitude larger than that of the distorted-tetrahedral geometry, leading to a much smaller emission quantum yield (Phi = 0.009) at 298 K. Since the flattening motion is markedly suppressed below 130 K, the emission observed in 2mTHF below 130 K is considered to occur principally from the (M + X)LCT state with a distorted-tetrahedral geometry. To interpret the photophysics of 1 and 4 in both the solid and solution states, we have proposed the "2-conformations with 2-spin-states model (2C x 2S model)". The electroluminescence device using (1) as a green emissive dopant showed a moderate EL efficiency; luminous efficiency = 10.4 cd/A, power efficiency = 4.2 lm/W at 93 cd/m(2), and maximum external quantum efficiency = 4.8%.     

Highly luminescent half-lantern cyclometalated platinum(II) complex: synthesis, structure, luminescence studies, and reactivity

The half-lantern compound [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)]·Me(2)CO (1) was obtained by reaction of equimolar amounts of potassium 2-mercaptobenzothiazolate (KC(7)H(4)NS(2)) and [Pt(bzq)(NCMe)(2)]ClO(4). The Pt(II)···Pt(II) separation in the neutral complex [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)] is 2.910 (2) ?, this being among the shortest observed in half-lantern divalent platinum complexes. Within the complex, the benzo[h]quinoline (bzq) groups lie in close proximity with most C···C distances being between 3.3 and 3.7 ?, which is indicative of significant π-π interactions. The reaction of 1 with halogens X(2) (X(2) = Cl(2), Br(2), or I(2)) proceeds with a two-electron oxidation to give the corresponding dihalodiplatinum(III) complexes [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)X}(2)] (X = Cl 2, Br 3, I 4). Their X-ray structures confirm the retention of the half-lantern structure and the coordination mode of the bzq and the bridging ligand μ-C(7)H(4)NS(2)-κN,S. The Pt-Pt distances (Pt-Pt = 2.6420(3) ? 2, 2.6435(4) ? 3, 2.6690(3) ? 4) are shorter than that in 1 because of the Pt-Pt bond formation. Time dependent-density functional theory (TD-DFT) studies performed on 1 show a formal bond order of 0 between the metal atoms, with the 6p(z) contribution diminishing the antibonding character of the highest occupied molecular orbital (HOMO) and being responsible for an attractive intermetallic interaction. A shortening of the Pt-Pt distance from 2.959 ? in the ground state S(0) to 2.760 ? in the optimized first excited state (T(1)) is consistent with an increase in the Pt-Pt bond order to 0.5. In agreement with TD-DFT calculations, the intense, structureless, red emission of 1 in the solid state and in solution can be mainly attributed to triplet metal-metal-to-ligand charge transfer ((3)MMLCT) [dσ*(Pt-Pt) → π*(bzq)] excited states. The high quantum yields of this emission measured in toluene (44%) and solid state (62%) at room temperature indicate that 1 is a very efficient and stable (3)MMLCT emitter, even in solution. The high luminescence quantum yield of its red emission, added to its neutral character and the thermal stability of 1, make it a potential compound to be incorporated as phosphorescent dopant in multilayer organic light-emitting devices (OLEDs).     

Luminescent platinum(II) complexes containing isoquinolinyl indazolate ligands: synthetic reaction pathway and photophysical properties

New Pt(II) dichloride complexes [Pt(1-iqdzH)Cl2] (2a) and [Pt(3-iqdzH)Cl2] (2b), in which idqzH = 1- or 3-isoquinolinyl indazole, were prepared by treatment of the corresponding indazoles with K2PtCl4 in aqueous HCl solution. Despite their nonemissive nature, these complexes could react with excess indazole, sodium picolinate, and 3-trifluoromethyl-5-(2-pyridyl) pyrazole [(fppz)H] to afford the respective a and b series of luminescent complexes [Pt(1-iqdz)(L/\X)] and [Pt(3-iqdz)(L/\X)], where L/\X = 1-iqdz (1a), 3-iqdz (1b), pic (3a, 3b), and fppz (4a, 4b). Single-crystal X-ray diffraction studies of 1b, 2a, and 3b revealed a planar molecular geometry without notable intermolecular Pt...Pt contact in the solid crystal, a result of the steric repulsion imposed by the bulky indazole fragments. For coordination complexes 1, 3, and 4, photoluminescence in degassed CH2Cl2 revealed high quantum efficiency and short radiative lifetimes in the range of several microseconds. As supported by the spectral feature, the associated radiation lifetimes, and a computational approach based on time-dependent density function theory (TD-DFT), the origin of the emission is attributed to a mixed 3MLCT/3pipi transition. The TD-DFT approach further confirmed that, except for the series 1 complexes, the HOMO of 3-iqdz complexes 3b and 4b is much less located at the central Pt(II) atom than the HOMO orbitals of the respective 1-iqdz complexes 3a and 4a, leading to a smaller degree of MLCT contribution. Consequently, there are a blue-shifted emission signal and an inferior emission quantum yield for the 3-iqdz derivatives. OLED devices with a multilayer configuration of ITO/NPB/CBP:3a/BCP/Alq3/LiF/Al were fabricated using a CBP layer doped with various concentrations of 3a, ranging from 6% to 100%, within the emitting layer. The best device performance was realized using a 6% doping concentration, for which the external quantum yield of 4.93%, luminous efficiency of 12.19 cd/A, and power efficiency of 6.12 lm W-1 were observed at 20 mA/cm2, while a maximum luminescence as high as 20296 cd/m2 was also realized at 16 V, showing good prospect for the fabrication of Pt(II) based OLEDs.     

Mechanism of CO exchange on cis-[M(CO)2X2]- complexes (M=Rh,Ir;X=Cl, Br, or I)

The CO exchange on cis-[M(CO)2X2]- with M = Ir (X = Cl, la; X = Br, 1b; X = I, 1c) and M = Rh (X = Cl, 2a; X = Br, 2b; X = I, 2c) was studied in dichloromethane. The exchange reaction [cis-[M(CO)2X2]- + 2*CO is in equilibrium cis-[M(*CO)2X2]- + 2CO (exchange rate constant: kobs)] was followed as a function of temperature and carbon monoxide concentration (up to 6 MPa) using homemade high gas pressure NMR sapphire tubes. The reaction is first order for both CO and cis-[M(CO)2X2]- concentrations. The second-order rate constant, k2(298) (=kobs)[CO]), the enthalpy, deltaH*, and the entropy of activation, deltaS*, obtained for the six complexes are respectively as follows: la, (1.08 +/- 0.01) x 10(3) L mol(-1) s(-1), 15.37 +/- 0.3 kJ mol(-1), -135.3 +/- 1 J mol(-1) K(-1); 1b, (12.7 +/- 0.2) x 10(3) L mol(-1) s(-1), 13.26 +/- 0.5 kJ mol(-1), -121.9 +/- 2 J mol(-1) K(-1); 1c, (98.9 +/- 1.4) x 10(3) L mol(-1) s(-1), 12.50 +/- 0.6 kJ mol(-1), -107.4 +/- 2 J mol(-1) K(-1); 2a, (1.62 +/- 0.02) x 10(3) L mol(-1) s(-1), 17.47 +/- 0.4 kJ mol(-1), -124.9 +/- 1 J mol(-1) K(-1); 2b, (24.8 +/- 0.2) x 10(3) L mol(-1) s(-1), 11.35 +/- 0.4 kJ mol(-1), -122.7 +/- 1 J mol(-1) K(-1); 2c, (850 +/- 120) x 10(3) L mol(-1), s(-1), 9.87 +/- 0.8 kJ mol(-1), -98.3 +/- 4 J mol(-1) K(-1). For complexes la and 2a, the volumes of activation were measured and are -20.9 +/- 1.2 cm3 mol(-1) (332.0 K) and -17.2 +/- 1.0 cm3 mol(-1) (330.8 K), respectively. The second-order kinetics and the large negative values of the entropies and volumes of activation point to a limiting associative, A, exchange mechanism. The reactivity of CO exchange follows the increasing trans effect of the halogens (Cl < Br < I), and this is observed on both metal centers. For the same halogen, the rhodium complex is more reactive than the iridium complex. This reactivity difference between rhodium and iridium is less marked for chloride (1.5: 1) than for iodide (8.6:1) at 298 K.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.     

Ring-opening reactions induced by gold(I) of five- and four-coordinate palladium(II) and platinum(II) complexes containing tripodal or linear polyphosphines

The tripodal ligands NP(3)(tris[2-(diphenylphosphino)ethyl]amine) and PP(3)(tris[2-(diphenylphosphino)ethyl]phosphine), form five-coordinate [Pd(NP(3))X]X [X = Cl (1), Br (2)], [M(PP(3))X]X [M = Pd: X = Cl (4), Br (5), I (6); M = Pt, X = Cl (7), Br (8), I (9)] and four-coordinate[Pd(NP(3))I]I (3) complexes containing three fused rings around the metal. The interaction between Au(tdg)X (tdg = thiodiglycol; X = Cl, Br) or AuI and the respective ionic halo complexes 1-9 in a 1:1 stoichiometric ratio occurs via a ring-opening reaction with formation of the heterobimetallic systems PdAu(NP(3))X(3)[X = Cl (11), Br (12), I (13)], [MAu(PP(3))X(2)]X [M = Pd: X = Cl (14), Br (15), I (16); M = Pt: X = Cl (17), Br (18), I (19)]. The cations of complexes 17 and 18 were shown, by X-ray diffraction, to contain a distorted square-planar Pt(II) arrangement (Pt(P(2)P)X) where PP(3) is acting as tridentate chelating ligand and an almost linear PAuX moiety bearing the dangling phosphorus formed in the ring-opening process. PPh(3) coordinates to Au(I) and not to M(II) when added in excess to 14 and 17. Complexes 14-17 and [Pt(P(4))](BPh(4))(2) (10) (P4=linear tetraphosphine) also react with A(I), via chelate ring-openings to give MAu(2)(PP(3))X(4) [M = Pd: X = Cl (20), Br (21), I (22); M = Pt: X = Cl (23)] and [Pt(2)Au(2)(mu-Cl)(2)(mu-P(4))(2)](BPh(4))(4) (24), respectively.     

Substituent effect on the photophysical properties, electrochemical properties and electroluminescence performance of orange-emitting iridium complexes

A series of bis(2-phenylbenzothiozolato-N,C(2'))iridium(acetylacetonate) [(bt)(2)Ir(acac)] derivatives, 1-4, were synthesized. Different substituents (CF(3), F, CH(3), OCH(3)) were introduced in the benzothiazole ring to study the substituent effect on the photophysical, electrochemical properties and electroluminescent performance of the complexes, and finally to select high-performance phosphors for use in organic light-emitting diodes (OLEDs). All complexes 1-4 and (bt)(2)Ir(acac) are orange-emitting with tiny spectral difference, despite the variation of the substituent. However, the phosphorescent quantum yield increases with the electron-withdrawing ability of the substituent. This is in contrast to the previous observation that the substituent in the phenyl ring bonded to the metal center of (bt)(2)Ir(acac) not only affected the luminescent quantum efficiency but also greatly tuned the emission color of the complexes. Quantum chemical calculations revealed that the substituents in this position do not make a significant contribution to both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), which probably accounts for the fact that they do no strongly influence the bandgap and emission color of the complexes. Orange OLEDs were fabricated using 1-4 as doped emitters. The electron-withdrawing CF(3) and F groups favor improving the electroluminescence efficiency in comparison with that of the parent (bt)(2)Ir(acac), while electron-donating CH(3) and OCH(3) are not favorable for light emission. The complex 1 based OLED exhibited a maximum luminance efficiency of 54.1 cd A(-1) (a power efficiency of 24 lm W(-1) and an external quantum efficiency of 20%), which are among the best results ever reported for vacuum deposited orange OLEDs so far.     

Synthesis, photophysical and electrophosphorescent properties of fluorene-based platinum(II) complexes

A series of platinum(II) complexes bearing tridentate cyclometalated C^N^N (C^N^N=6-phenyl-2,2'-bipyridine and π-extended R-C^N^N=3-[6'-(naphthalen-2'-yl)pyridin-2'-yl]isoquinoline) ligands with fluorene units have been synthesised and their photophysical properties have been studied. The fluorene units are incorporated into the cyclometalated ligands by a Suzuki coupling reaction. An increase in the π-conjugation of the cyclometalated ligands confers favourable photophysical properties compared to the 6-phenyl-2,2'-bipyridine analogues. The fluorene-based platinum(II) complexes display vibronic-structured emission bands with λ(max)=558-601 nm, and high emission quantum yields up to 0.76 in degassed dichloromethane. Their emissions are tentatively assigned to excited states with mixed (3)IL/(3)MLCT parentage (IL=intraligand, MLCT=metal-to-ligand charge transfer). The crystal structures of these platinum(II) complexes reveal extensive Pt(II)···π and/or π-π interactions. The fluorene-based platinum(II) complexes are soluble in organic solvents, have high thermal stability with decomposition temperature >350 °C, and can be thermally vacuum-sublimed or solution-processed as phosphorescent dopants for the fabrication of organic light-emitting diodes (OLEDs). A monochromic OLED with 3d as dopant (2 wt%) fabricated by vacuum deposition gave a current efficiency of 14.7 cd A(-1) and maximum brightness of 27000 cd m(-2). A high current efficiency (9.2 cd A(-1)) has been achieved in a solution-processed OLED using complex 3f (5 wt%) doped in a PVK (poly(9-vinylcarbazole)) host.     

Highly phosphorescent bis-cyclometalated iridium complexes: synthesis, photophysical characterization, and use in organic light emitting diodes.

The synthesis and photophysical study of a family of cyclometalated iridium(III) complexes are reported. The iridium complexes have two cyclometalated (C(**)N) ligands and a single monoanionic, bidentate ancillary ligand (LX), i.e., C(**)N2Ir(LX). The C(**)N ligands can be any of a wide variety of organometallic ligands. The LX ligands used for this study were all beta-diketonates, with the major emphasis placed on acetylacetonate (acac) complexes. The majority of the C(**)N2Ir(acac) complexes phosphoresce with high quantum efficiencies (solution quantum yields, 0.1-0.6), and microsecond lifetimes (e.g., 1-14 micros). The strongly allowed phosphorescence in these complexes is the result of significant spin-orbit coupling of the Ir center. The lowest energy (emissive) excited state in these C(**)N2Ir(acac) complexes is a mixture of (3)MLCT and (3)(pi-pi) states. By choosing the appropriate C(**)N ligand, C(**)N2Ir(acac) complexes can be prepared which emit in any color from green to red. Simple, systematic changes in the C(**)N ligands, which lead to bathochromic shifts of the free ligands, lead to similar bathochromic shifts in the Ir complexes of the same ligands, consistent with "C(**)N2Ir"-centered emission. Three of the C(**)N2Ir(acac) complexes were used as dopants for organic light emitting diodes (OLEDs). The three Ir complexes, i.e., bis(2-phenylpyridinato-N,C2')iridium(acetylacetonate) [ppy2Ir(acac)], bis(2-phenyl benzothiozolato-N,C2')iridium(acetylacetonate) [bt2Ir(acac)], and bis(2-(2'-benzothienyl)pyridinato-N,C3')iridium(acetylacetonate) [btp2Ir(acac)], were doped into the emissive region of multilayer, vapor-deposited OLEDs. The ppy2Ir(acac)-, bt2Ir(acac)-, and btp2Ir(acac)-based OLEDs give green, yellow, and red electroluminescence, respectively, with very similar current-voltage characteristics. The OLEDs give high external quantum efficiencies, ranging from 6 to 12.3%, with the ppy2Ir(acac) giving the highest efficiency (12.3%, 38 lm/W, >50 Cd/A). The btp2Ir(acac)-based device gives saturated red emission with a quantum efficiency of 6.5% and a luminance efficiency of 2.2 lm/W. These C(**)N2Ir(acac)-doped OLEDs show some of the highest efficiencies reported for organic light emitting diodes. The high efficiencies result from efficient trapping and radiative relaxation of the singlet and triplet excitons formed in the electroluminescent process.     

2-[(二苯基膦基)甲基]吡啶铜(I)配合物的合成及光物理和电致发光性质

合成了3个2-[(二苯基膦基)甲基]吡啶(L)铜(Ⅰ)配合物：Cu(L)2(BF4)(a)、Cu(L)(PPh3)2(BF4)(b)和Cu(L)(POP)(BF4)(c)(POP为双[(2-二苯膦基)苯基]醚),其组成和结构分别经1H NMR、31P NMR、元素分析及晶体结构分析确证。 分子中,中心铜(Ⅰ)离子均为扭曲的四面体配位构型。 在除气的二氯甲烷溶液中,配合物均出现261~274 nm强π-π*吸收,未见明显的Cu→L电荷转移(MLCT)跃迁吸收。 配合物的薄膜样品发射蓝绿光,最大发射峰分别在515、476和481 nm处,光致发光效率分别为16.0%、12.9%和7.0%。 以聚乙烯咔唑(PVK)与配合物b为发光层的多层电致发光器件,当电流密度为1.0×10-3 A/cm2时,电致发光的电流效率为0.36 cd/A,最大亮度为217 cd/m2。     

Anionic Halomolybdate(III) Chemistry. Tetrahydrofuran Loss from [MoX(3)Y(THF)(2)](-) (X, Y = Cl, Br, I), Preparation and Properties of [Mo(3)X(12)](3)(-) (X = Br, I), and Crystal Structure of the Edge-Sharing Trioctahedral [PPh(4)](3)[Mo(3)I(12)

By interaction of MoX(3)(THF)(3) with [Cat]X in THF, the salts [Cat][MoX(4)(THF)(2)] have been synthesized [X = I, Cat = PPh(4), NBu(4), NPr(4), (Ph(3)P)(2)N; X = Br, Cat = NBu(4), PPh(4) (Ph(3)P)(2)N]. Mixed-halide species [MoX(3)Y(THF)(2)](-) (X, Y = Cl, Br, I) have also been generated in solution and investigated by (1)H-NMR. When the tetraiodo, tetrabromo, and mixed bromoiodo salts are dissolved in CH(2)Cl(2), clean loss of all coordinated THF is observed by (1)H-NMR. On the other hand, [MoCl(4)(THF)(2)](-) loses only 1.5 THF/Mo. The salts [Cat](3)[Mo(3)X(12)] (X = Br, I) have been isolated from [Cat][MoX(4)(THF)(2)] or by running the reaction between MoX(3)(THF)(3) and [Cat]X directly in CH(2)Cl(2). The crystal structure of [PPh(4)](3)[Mo(3)I(12)] exhibits a linear face-sharing trioctahedron for the trianion: triclinic, space group P&onemacr;; a = 11.385(2), b = 12.697(3), c = 16.849(2) ?; alpha = 76.65(2), beta = 71.967(12), gamma = 84.56(2) degrees; Z = 1; 431 parameters and 3957 data with I > 2sigma(I). The metal-metal distance is 3.258(2) ?. Structural and magnetic data are consistent with the presence of a metal-metal sigma bond order of (1)/(2) and with the remaining 7 electrons being located in 7 substantially nonbonding orbitals. The ground state of the molecule is predicted to be subject to a Jahn-Teller distortion, which is experimentally apparent from the nature of the thermal ellipsoid of the central Mo atom. The [Mo(3)X(12)](3)(-) ions reacts with phosphines (PMe(3), dppe) to form products of lower nuclearity by rupture of the bridging Mo-X bonds.     

Kinetics and mechanisms of the oxidation of iodide and bromide in aqueous solutions by a trans-dioxoruthenium(VI) complex

The kinetics and mechanisms of the oxidation of I (-) and Br (-) by trans-[Ru (VI)(N 2O 2)(O) 2] (2+) have been investigated in aqueous solutions. The reactions have the following stoichiometry: trans-[Ru (VI)(N 2O 2)(O) 2] (2+) + 3X (-) + 2H (+) --> trans-[Ru (IV)(N 2O 2)(O)(OH 2)] (2+) + X 3 (-) (X = Br, I). In the oxidation of I (-) the I 3 (-)is produced in two distinct phases. The first phase produces 45% of I 3 (-) with the rate law d[I 3 (-)]/dt = ( k a + k b[H (+)])[Ru (VI)][I (-)]. The remaining I 3 (-) is produced in the second phase which is much slower, and it follows first-order kinetics but the rate constant is independent of [I (-)], [H (+)], and ionic strength. In the proposed mechanism the first phase involves formation of a charge-transfer complex between Ru (VI) and I (-), which then undergoes a parallel acid-catalyzed oxygen atom transfer to produce [Ru (IV)(N 2O 2)(O)(OHI)] (2+), and a one electron transfer to give [Ru (V)(N 2O 2)(O)(OH)] (2+) and I (*). [Ru (V)(N 2O 2)(O)(OH)] (2+) is a stronger oxidant than [Ru (VI)(N 2O 2)(O) 2] (2+) and will rapidly oxidize another I (-) to I (*). In the second phase the [Ru (IV)(N 2O 2)(O)(OHI)] (2+) undergoes rate-limiting aquation to produce HOI which reacts rapidly with I (-) to produce I 2. In the oxidation of Br (-) the rate law is -d[Ru (VI)]/d t = {( k a2 + k b2[H (+)]) + ( k a3 + k b3[H (+)]) [Br (-)]}[Ru (VI)][Br (-)]. At 298.0 K and I = 0.1 M, k a2 = (2.03 +/- 0.03) x 10 (-2) M (-1) s (-1), k b2 = (1.50 +/- 0.07) x 10 (-1) M (-2) s (-1), k a3 = (7.22 +/- 2.19) x 10 (-1) M (-2) s (-1) and k b3 = (4.85 +/- 0.04) x 10 (2) M (-3) s (-1). The proposed mechanism involves initial oxygen atom transfer from trans-[Ru (VI)(N 2O 2)(O) 2] (2+) to Br (-) to give trans-[Ru (IV)(N 2O 2)(O)(OBr)] (+), which then undergoes parallel aquation and oxidation of Br (-), and both reactions are acid-catalyzed.     

Facile Halogenation of Pyrazolate‐Bridged Copper(I) Complexes: Synthesis,Crystal Structure,and Photoluminescent Properties

Solvothermal reactions of 3,5‐dimethylpyrazole (Me₂pz), and CuX in MeOH afforded two trinuclear complexes [Cu(XMe₂pz)]₃ [X = I ( 1 ); Br ( 2 )], where the halogenated ligand XMe₂pz in 1 and 2 were in‐situ formed from the reaction of Me₂pz with X^–. The crystal structure of 1 was determined by X‐ray crystallography. It turned out that it has a classic [Cu₃N₆] unit. The luminescence properties of 1 and 2 were investigated and the results show that both complexes have high photoluminescence quantum yields of 62 % and 84 % and long lifetimes of 21.7 μs and 30.5 μs, respectively.     

PX4+, P2X5+, and P5X2+ (X=Br,I) salts of the superweak Al(OR)4- anion [R=C(CF3)3

PX(4) (+)[Al(OR)(4)](-) (X=I: 1 a, X=Br: 1 b) was prepared from X(2), PX(3), and Ag[Al(OR)(4)] [R=C(CF(3))(3)] in CH(2)Cl(2) at -30 degrees C in 69-86 % yield. P(2)X(5) (+) salts were prepared from 2 PX(3) and Ag[Al(OR)(4)] in CH(2)Cl(2) at -30 degrees C yielding almost quantitatively P(2)X(5) (+)[Al(OR)(4)](-) (X=I: 3 a, X=Br: 3 b). The phosphorus-rich P(5)X(2) (+) salts arose from the reaction of cold (-78 degrees C) mixtures of PX(3), P(4), and Ag[Al(OR)(4)] giving P(5)X(2) (+)[Al(OR)(4)](-) (X=I: 4 a, X=Br: 4 b) with a C(2v)-symmetric P(5) cage. Silver salt metathesis presumably generated unstable PX(2) (+) cations from PX(3) and Ag[Al(OR)(4)] (X=Br, I) that acted as electrophilic carbene analogues and inserted into the Xbond;X (Pbond;X/Pbond;P) bond of X(2) (PX(3)/P(4)) leading to the highly electrophilic and CH(2)Cl(2)-soluble PX(4) (+) (P(2)X(5) (+)/P(5)X(2) (+)) salts. Reactions that aimed to synthesize P(2)I(3) (+) from P(2)I(4) and Ag[Al(OR)(4)] instead led to anion decomposition and the formation of P(2)I(5)(CS(2))(+)[(RO)(3)Al-F-Al(OR)(3)](-) (5). All salts were characterized by variable-temperature solution NMR studies (3 b also by (31)P MAS NMR), Raman and/or IR spectroscopy as well as X-ray crystallography (with the exception of 4 a). The thermochemical volumes of the Pbond;X cations are 121 (PBr(4) (+)), 161 (PI(4) (+)), 194 (P(2)Br(5) (+)), 271 (P(2)I(5) (+)), and 180 A(3) (P(5)Br(2) (+)). The observed reactions were fully accounted for by thermochemical calculations based on (RI-)MP2/TZVPP ab initio results and COSMO solvation enthalpy calculations (CH(2)Cl(2) solution). The enthalpies of formation of the gaseous Pbond;X cations were derived as +764 (PI(4) (+)), +617 (PBr(4) (+)), +749 (P(2)I(5) (+)), +579 (P(2)Br(5) (+)), +762 (P(5)I(2) (+)), and +705 kJ mol(-1) (P(5)Br(2) (+)). The insertion of the intermediately prepared carbene analogue PX(2) (+) cations into the respective bonds were calculated, at the (RI-)MP2/TZVPP level, to be exergonic at 298 K in CH(2)Cl(2) by Delta(r)G(CH(2)Cl(2))=-133.5 (PI(4) (+)), -183.9 (PBr(4) (+)), -106.5 (P(2)I(5) (+)), -81.5 (P(2)Br(5) (+)), -113.2 (P(5)I(2) (+)), and -114.5 kJ mol(-1) (P(5)Br(2) (+)).     

7Li NMR studies on complexation reactions of lithium ion with cryptand C211 in ionic liquids: comparison with corresponding reactions in nonaqueous solvents

(7)Li NMR spectra of DEME-TFSA [DEME=N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium; TFSA=bis(trifluoromethanesulfonyl)amide], EMI-TFSA (EMI=1-ethyl-3-methylimidazolium), MPP-TFSA (MPP = N-methyl-N-propylpyridinium), DEME-PFSA [PFSA=bis(pentafluoroethanesulfonyl)amide], and DEME-HFSA [HFSA=bis(heptafluoropropanesulfonyl)amide] ionic liquid (IL) solutions containing LiX (X=TFSA, PFSA, or HFSA) and C211 (4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane) were measured at various temperatures. As a result, it was found that the uncomplexed Li(I) species existing as [Li(X)(2)](-) in the present ILs exchange with the complexed Li(I) ([Li·C211](+)) and that the exchange reactions proceed through the bimolecular mechanism, [Li·C211](+) + [*Li(X)(2)](-)=[*Li·C211](+) + [Li(X)(2)](-). Kinetic parameters [k(s)/(kg m(-1) s(-1)) at 25 °C, ΔH(++)/(kJ mol(-1)), ΔS(++)/(J K(-1) mol(-1))] are as follows: 5.57×10(-2), 69.8 ± 0.4, and -34.9 ± 1.0 for the DEME-TFSA system; 5.77×10(-2), 70.6 ± 0.2, and -31.9 ± 0.6 for the EMI-TFSA system, 6.13×10(-2), 69.0 ± 0.3, and -36.7 ± 0.7 for the MPP-TFSA system; 1.35 × 10(-1), 65.2 ± 0.5, and -43.1 ± 1.4 for the DEME-PFSA system; 1.14×10(-1), 64.4 ± 0.3, and -47.1 ± 0.6 for the DEME-HFSA system. To compare these kinetic data with those in conventional nonaqueous solvents, the exchange reactions of Li(I) between [Li·C211](+) and solvated Li(I) in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) were also examined. These Li(I) exchange reactions were found to be independent of the concentrations of the solvated Li(I) and hence proposed to proceed through the dissociative mechanism. Kinetic parameters [k(s)/s(-1) at 25 °C, ΔH(++)/(kJ mol(-1)), ΔS(++)/(J K(-1) mol(-1))] are as follows: 1.10 × 10(-2), 68.9 ± 0.2, and -51.3 ± 0.4 for the DMF system; 1.13×10(-2), 76.3 ± 0.3, and -26.3 ± 0.8 for the DMSO system. The differences in reactivities between ILs and nonaqueous solvents were proposed to be attributed to those in the chemical forms of the uncomplexed Li(I) species, i.e., the negatively charged species ([Li(X)(2)](-)) in ILs, and the positively charged ones ([Li(solvent)(n)](+)) in nonaqueous solvents.     

Efficient singlet oxygen generation by luminescent 2-(2′-thienyl)pyridyl cyclometalated platinum(II) complexes and their calixarene derivatives

Luminescent cyclometalated platinum(II) complexes, namely [Pt(Thpy)(PPh₃)X]ⁿ⁺ (HThpy = 2-(2′-thienyl)pyridine; X = Cl⁻ ( 1 ), n = 0; X = CH₃CN ( 2 ), pyridine ( 3 ), n = 1) and [Pt(Thpy)(HThpy)Y] ^{n +} (Y = Cl⁻ ( 4 ), n = 0; Y = pyridine ( 5 ), n = 1), exhibit structured emission with peak maximum at ∼556 and 598 nm in degassed acetonitrile and with emission quantum yield and lifetime of up to 0.38 and 26 μs, respectively. These complexes are efficient photosensitizers of singlet oxygen with yields up to >90%. Complex 5 exhibited photocytotoxicity towards cancer cells and fluorescence microscopic images of cells incubated with 5 reveal substantial uptake at the nucleus and mitochondria.     

Construction of halide-bridged tungsten-copper-sulfide double cubanelike clusters from a new precursor [(Tp*WS2)2(μ-S2)

Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)](2) (3), [{Tp*W(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{Tp*W(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a [Cu(MeCN)(μ-Cl)(2)](+) bridge. For 4, one [Tp*W(μ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(μ(3)-S)(3)Cu(3)Br](+) cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)](4+) species. For 6 and 7, two [Tp*W(μ(3)-S)(3)Cu(3)X](+) cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.     

Electron-Transfer Reactions of Re(CO)(5): Atom-Transfer-Concerted Mechanism vs Bimetallic Intermediate Formation

Flash photochemically generated Re(CO)(5) reacts with halide complexes, Cu(Me(4)[14]-1,3,8,10-tetraeneN(4))X(+), Cu(Me(2)pyo[14]trieneN(4))X(+), and Ni(Me(2)pyo[14]trieneN(4))X(+) (X = Cl, Br, I) and ion pairs, [Co(bipy)(3)(3+), X(-)]. The rate constants for the electron transfers have values, k approximately 10(9) M(-1) s(-1), close to expectations for processes with diffusion-controlled rates. Reaction intermediates, probably bimetallic species, were detected in electron-transfer reactions of Re(CO)(5) with Cu(Me(6)[14]dieneN(4))X(+), (X = Cl, Br, I). In the absence of the halides X(-), the electron-transfer reactions between Re(CO)(5) and these complexes are slow, k < 10(6) M(-1) s(-1). The results are discussed in terms of inner-sphere pathways, namely an atom-transfer-concerted mechanism. The mediation of bimetallic intermediates in the electron transfer is also considered.     

A single-molecule excimer-emitting compound for highly efficient fluorescent organic light-emitting devices

A pyrene-containing single-molecule excimer-emitting compound, 1,8-bis(pyren-2-yl)naphthalene (BPyN), was synthesized. With BPyN as a host emitter, C545T-based green OLEDs were fabricated, exhibiting high efficiencies of 22 lm W(-1), 22 cd A(-1) and 6.2% external quantum efficiency (EQE) at 100 cd m(-2), and 19 lm W(-1), 22 cd A(-1) and 6.2% EQE at 1000 cd m(-2).     

Neutral copper(I) phosphorescent complexes from their ionic counterparts with 2-(2'-quinolyl)benzimidazole and phosphine mixed ligands

Neutral mononuclear Cu(I) complexes and their counterparts with counterion, i.e. Cu(qbm)(PPh(3))(2), Cu(qbm)(DPEphos), [Cu(Hqbm)(PPh(3))(2)](BF(4)) and [Cu(Hqbm)(DPEphos)](BF(4)), where Hqbm = 2-(2'-quinolyl)benzimidazole, DPEphos = bis[2-(diphenylphosphino)phenyl]ether, have been synthesized and characterized by X-ray structure analyses. All of the four complexes in solid state exhibit a strong phosphorescence band in the orange spectral region at room temperature. The photophysical properties of these complexes in both methylene chloride solution and poly(methyl methacrylate) film have been studied. Compared to the related cationic complexes, the neutral ones show blue-shifted emissions and longer lifetimes that can be attributed to the additional ligand-centered π-π* transition beside traditional metal-to-ligand charge-transfer (MLCT). By doping these complexes in N-(4-(carbazol-9-yl)phenyl)-3,6-bis(carbazol-9-yl) carbazole (TCCz), multilayer organic light-emitting diodes (OLEDs) were fabricated with the device structure of ITO/PEDOT/TCCz: Cu(I) (10 wt%)/BCP/Alq(3)/LiF/Al. The neutral complex Cu(qbm)(DPEphos) exhibits a higher current efficiency, up to 8.87 cd A(-1), than that (5.58 cd A(-1)) of its counterpart [Cu(Hqbm)(DPEphos)](BF(4)).