Synthese und Charakterisierung von Metallocen-Chelaten heterocyclischer 1,2-Dithiolate

Synthesis and Characterization of Metallocene Chelates of Heterocyclic 1,2-Dithiolates Synthesis and properties of metalocene dithiolene chelates Cp₂ML with metal(IV) ions (M) of group IVA (Ti, Zr, Hf) and of vanadium with L = dmit (1,3-dithiole-2-thione-4,5-dithiolate), dmt (1,2-dithiole-3-thione-4,5-dithiolate), dmid (1,3-dithiole-2-one-4,5-dithiolate) and dmise (1,3-dithiole-2-selone-4,5-dithiolate) are described. The structures of these compounds were discussed using IR-, UV/VIS-, ¹H-NMR-, ¹³C-NMR- and EPR data. The activation parameters of the chelate ring inversion of titanocene dithiolenes (Cp₂TiL) and the x-ray structure of Cp₂Ti(dmid) are given.     

Zur Koordinationschemie des 1,3-Dithiol-2-thion-4,5-diselenolats (dsit) – ein Vergleich mit 1,3-Dithiol-2-thion-4,5-dithiolat (dmit)

Coordination Chemistry of 1,3-Dithiole-2-thione-4,5-diselenolate (dsit) — Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) Synthesis and properties of metal(II) and/or metal(III) bis-chelates of 1,3-dithiole-2-thione-4,5-diselenolate (dsit) of general type (Bu₄N)_n[M(dsit)₂] (n = 2: M ? Zn, Cd, Hg, Cu, Ni, Pd, Pt; n = 1: M ? Ni, Au) are described. By comparison of the ir, ¹³C nmr, epr spectra, cyclovoltammetric data, and x-ray investigations (nickel-bis-chelates) of chelates of dsit and those of the chelates of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of selenium for sulfur substitution on position 4 and 5 of the heterocyclic ligand are discussed.     

A family of oxo-chalcogenide molybdenum and tungsten complexes, (n-Bu4N)2[M2O2(mu-Q)2(1,3-dithiole-2-thione-4,5-dithiolate)2] (M = Mo, W; Q = S, Se): new synthetic entries, structure, and gas-phase behavior

A new series of complexes with the general formula (n-Bu4N)2[M2O2(micro-Q)2(dmit)2] (where M = Mo, W; Q = S, Se; dmit = 1,3-dithiole-2-thione-4,5-dithiolate) have been prepared. Fragmentation of the trinuclear cluster (n-Bu4N)2[Mo3(micro3-S)(micro-S2)3(dmit)3] in the presence of triphenylphosphine (PPh3) gives the dinuclear compound (n-Bu4N)2[Mo2O2(micro-S)2(dmit)2] [(n-Bu4N)2[2]], which is formed via oxidation in air from the intermediate (n-Bu4N)2[Mo3(micro3-S)(micro-S)3(dmit)3] [(n-Bu4N)2[1]] complex. Ligand substitution of the molybdenum sulfur bridged [Mo2O2(micro-S)2(dimethylformamide)6]2+ dimer with the sodium salt of the dmit dithiolate also affords the dianionic compound (n-Bu4N)2[2]. The whole series, (n-Bu4N)2[Mo2O2(micro-Se)2(dmit)2] [(n-Bu4N)2[3]], (n-Bu4N)2[W2O2(micro-S)2(dmit)2] [(n-Bu4N)2[4]], (n-Bu4N)2[W2O2(micro-Se)2(dmit)2] [(n-Bu4N)2[5]], and (n-Bu4N)2[Mo2O2(micro-S)2(dmid)2] [(n-Bu4N)2[6]; dmid = 1,3-dithiole-2-one-4,5-dithiolate], has been synthesized by the excision of the polymeric (Mo3Q7Br4)x phases with PPh3 or 1,2-bis(diphenylphosphanyl)ethane in acetonitrile followed by the dithiolene incorporation and further degradation in air. Direct evidence of the presence of the intermediates with the formula [M3Q4(dmit)3]2- (M = Mo, W; Q = S, Se) has been obtained by electrospray ionization mass spectrometry. The crystal structures of (n-Bu4N)2[1], (PPh4)2[Mo2O2(micro-S)2(dmit)2] [(PPh4)2[2]; PPh4 = tetraphenylphosphonium], (n-Bu4N)2[2], (n-Bu4N)2[4], (PPh4)2[W2O2(micro-Se)2(dmit)2] [(PPh4)2[5]], and (n-Bu4N)2[6] have been determined. A detailed study of the gas-phase behavior for compounds (n-Bu4N)2[2-6] shows an identical fragmentation pathway for the whole family that consists of a partial breaking of the two dithiolene ligands followed by the dissociation of the dinuclear cluster.     

Zur Koordinationschemie des 1,3-Thiaselenol-2-thion-4,5-dithiolats (dmits) – ein Vergleich mit 1,3-Dithiol-2-thion-4,5-dithiolat (dmit)

Coordination Chemistry of 1,3-Thiaselenole-2-thione-4,5-dithiolate (dmits) – Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) Synthesis and properties of metal(II) and/or metal(III)-bis-chelates of 1,3-thiaselenole-2-thione-4,5-dithiolate (dmits) of the general type (Bu₄N)_n[M(dmits)₂] (n = 2: M = Zn, Cd, Hg, Ni, Cu, Pd; n = 1: M = Au, Ni) are described. By comparison of the i.r., ¹³C-n.m.r., epr spectra and cyclovoltammetric data of chelates of dmits and those of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of the substitution of selenium for sulfur on position 3 of the heterocyclic ligand dmit are discussed.     

Redox-switchable chromophores based on metal (Ni, Pd, Pt) mixed-ligand dithiolene complexes showing molecular second-order nonlinear-optical activity

The synthesis and full characterization of the redox-active nickel triad mixed-ligand dithiolene complexes based on Bz(2)pipdt = 1,4-dibenzylpiperazine-3,2-dithione and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate ligands are reported. These complexes show a reversibly bleacheable solvatochromic peak and a remarkably high negative molecular first hyperpolarizability, whose values depend on the metal being highest for the platinum(II) compound.     

Synthese und Eigenschaften von molekularen Leitern auf der Basis von dmit-isologen Chelaten Kristall- und Molekülstruktur des Tetramethylammonium-bis-[bis-(1,3-dithiol-2-selon-4,5-diselenolato)nickelat]; [(CH3)4N][Ni(dsise)2]2

Syntheses and Properties of Molecular Conductors based on dmit isologous Chelates. Crystal and Molecular Structure of Tetramethylammonium-bis-[bis(1,3-dithiole-2-selone-4,5-diselenolato)nickelate]; [(CH₃)₄N] [Ni(dsise)₂]₂ Syntheses and properties of dichalcogenolate chelates of the general type [(CH₃)₄N]_n[ML₂] (n ≤ 2; M = Ni, Pd, Pt); L = dmit (1,3-dithiole-2-thione-4,5-dithiolate), dmise (1, 3-dithiole-2-selone-4,5-dithiolate), dsit (1, 3-dithiole-2-thione-4,5-diselenolate), dsise (1, 3-dithiole-2-selone-4,5-diselenolate), dsis (1, 3-diselenole-2-selone-4,5-diselenolate) are reported. The effects of the chalcogen atom variation in these chelates are discussed by using UV/VIS, IR, EPR, cyclovoltammetric and conductivity data. The x-ray structure of [(CH₃)₄N][Ni(dsise)₂]₂ (space group Pccn, a = 7.427(1), b = 39.144(5), c = 11.836(1) Å) and the conductivity of the crystal (12 S cm^?1 at room temperature) are given.     

1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基的不对称二硫纶金属(Cd,Zn)配合物的热行为和热分解反应动力学

用TG-DTG-DTA联用技术研究了两种1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基的不对称二硫纶金属(Cd,Zn)配合物在动态氮气气氛中的热行为,通过应用EDS技术和元素分析方法对热分解过程中各步反应中间体的组成进行了探索,并结合其物质结构进行了讨论。协同使用四种热分析动力学方法获得了各步反应的热分解动力学参数,并推断了它们的最可能分解反应机理。     

A density functional study of the highly adaptable molecular structure of Mo(V) and W(V) dithiolene complexes: from three-dimensional antiferromagnet to spin ladder

Cp2M(dithiolene) (M = MoIV, WIV) d2 complexes exhibit a folding (theta) of the MS2C2 metallacycle along the S-S axis upon oxidation to the d1 paramagnetic cation. The evolution of the peculiar unfolded structure (theta = 0 degree) of Cp2Mo(dmit).+ (dmit2-, 2-thioxo-1,3-dithiole-4,5-dithiolate) in its AsF6- salt toward the introduction of heavy atoms (W, Se) is examined here by substituting dsit2- (dsit2-, 2-thioxo-1,3-dithiole-4,5-diselenolate) for dmit2- and/or W for Mo in those AsF6- salts. While [Cp2Mo(dsit).+][AsF6-] (orthorhombic, Cmcm, a = 9.071(2), b = 20.868(4), c = 10.243(2) A, V = 1938.9(7) A3, Z = 4) and [Cp2W(dmit).+][AsF6-] (orthorhombic, Cmcm, a = 9.0295(15), b = 20.568(2), c = 10.2641(12) A, V = 1906.2(4) A3, Z = 4) crystallize with an unfolded geometry and are isostructural with [Cp2Mo(dmit).+][AsF6-], the introduction of both W and dsit2- in Cp2W(dsit) stabilizes a fully different structure for [Cp2W(dsit).+][AsF6-] (monoclinic, P2(1)/c, a = 6.8442, b = 15.9923(13), c = 17.6594(16) A, beta = 90.934(11) degrees, V = 1932.6(3) A3, Z = 4) with the Cp2W(dsit).+ cation in a folded geometry (theta = 30.1(1) degrees). DFT calculations show that the variety of folding angles and hence of molecular structures found in those open-shell d1 Cp2M(dithiolene).+ complexes is attributable to a very low energy cost (< 1 kcal mol-1) for folding around the minimal energy folding angle. The molecular geometry of those complexes and hence their frontier orbitals are therefore highly related to the actual crystal structure they adopt. The unfolded complexes exhibit, in their AsF6- salts, a three-dimensional set of intermolecular interactions in the solid state, confirmed by the presence of an antiferromagnetic ground state (TNéel = 3.5(5) K in [Cp2W(dmit).+][AsF6-]). On the other hand, the folding of Cp2W(dsit).+ in [Cp2W(dsit).+][AsF6-] leads to the formation of a rare spin-ladder system with a spin gap of 90-100 K, as deduced from the temperature dependence of its magnetic susceptibility.     

CpNi(dithiolene)] (and diselenolene) neutral radical complexes

Various preparations of the neutral radical [CpNi(dddt)] complex (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate) were investigated with CpNi sources, [Cp2Ni], [Cp2Ni](BF4), [CpNi(CO)]2, and [CpNi(cod)](BF4), and dithiolene transfer sources, O=C(dddt), the naked dithiolate (dddt(2-)), the monoanion of square-planar Ni dithiolene complex (NBu4)[Ni(dddt)2], and the neutral complex [Ni(dddt)2]. The reaction of [CpNi(cod)](BF4) with (NBu4)[Ni(dddt)2] gave the highest yield for the preparation of [CpNi(dddt)] (86%). [CpNi(ddds)] (ddds = 5,6-dihydro-1,4-dithiin-2,3-diselenolate), [CpNi(dsdt)] (dsdt = 5,6-dihydro-1,4-diselenin-2,3-dithiolate), [CpNi(bdt)] (bdt = 1,2-benzenedithiolate), and [CpNi(bds)] (bds = 1,2-benzenediselenolate) were synthesized by the reactions of [Cp2Ni] with the corresponding neutral Ni dithiolene complexes [Ni(ddds)2]2, [Ni(dsdt)2], [Ni(bdt)2], and [Ni(bds)2], respectively. The five, formally Ni(III), radical complexes oxidize and reduce reversibly. They exhibit, in the neutral state, a strong absorption in the NIR region, from 1000 nm in the dddt/ddds/dsdt series to 720 nm in the bdt/bds series with epsilon values between 2500 and 5000 M(-1) cm(-1). The molecular and solid state structures of the five complexes were determined by X-ray structure analyses. [CpNi(dddt)] and [CpNi(ddds)] are isostructural, while [CpNi(dsdt)] exhibits a closely related structure. Similarly, [CpNi(bdt)] and [CpNi(bds)] are also isostructural. Correlations between structural data and magnetic measurements show the presence of alternated spin chains in [CpNi(dddt)], [CpNi(ddds)], and [CpNi(dsdt)], while a remarkably strong antiferromagnetic interaction in [CpNi(bdt)] and [CpNi(bds)] is attributed to a Cp...Cp face-to-face sigma overlap, an original feature in organometallic radical complexes.     

Photooxidation of Transition Metal Complexes of 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) and 1,2-Dithiole-3-thione-4,5-dithiolate (dmt)

Metall(II) bis-chelates of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) and 1,2-dithiole-3-thione-4,5-dithiolate (dmt) undergo in CHCl₃/CH₃CN (ratio 1:24) photooxidation to the metal(III) bis-chelates when irradiated at 313 nm. No side reactions were observed. There is no correlation between the quantum yields of photooxidation and the electrochemical halve-wave potentials. This holds also in comparison to maleonitriledithiolato chelates.     

Two pressure-induced superconducting anion radical salts exhibiting different spin states at ambient pressure

Pressure-induced superconducting behavior was found in two anion radical salts, EtMe3Z[Pd(dmit)2]2 (dmit = 1,3-dithiole-2-thione-4,5-dithiolate, Z = P, As), that are Mott insulators and exhibit different magnetic and structural transitions at ambient pressure.     

Synthesis and Crystal Structure of 〔EDA〕〔Ni(dmit)_2〕_3

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Trinuclear Mo3S7 clusters coordinated to dithiolate or diselenolate ligands and their use in the preparation of magnetic single component molecular conductors

A general route for the preparation of a series of dianionic Mo3S7 cluster complexes bearing dithiolate or diselenolate ligands, namely, [Mo3S7L3](2-) (where L = tfd (bis(trifluoromethyl)-1,2-dithiolate) (4(2-)), bdt (1,2-benzenedithiolate) (5(2-)), dmid (1,3-dithia-2-one-4,5-dithiolate) (6(2-)), and dsit (1,3-dithia-2-thione-4,5-diselenolate) (7(2-))) is reported by direct reaction of [Mo3S7Br6](2-) and (n-Bu)2Sn(dithiolate). The redox properties, molecular structure, and electronic structure (BP86/VTZP) of the 4(2-) to 7(2-) clusters have also been investigated. The HOMO orbital in all complexes is delocalized over the ligand and the Mo3S7 cluster core. Ligand contributions to the HOMO range from 61.67% for 4(2-) to 82.07% for 7(2-), which would allow fine-tuning of the electronic and magnetic properties. These dianionic clusters present small energy gaps between the HOMO and HOMO-1 orbitals (0.277-0.104 eV). Complexes 6(2-) and 7(2-) are oxidized to the neutral state to afford microcrystalline or amorphous fine powders that exhibit semiconducting behavior and present antiferromagnetic exchange interactions. These compounds are new examples of the still rare single-component conductors based on cluster magnetic units.     

Synthesis,Crystal Structures and Intermolecular Magnetic Coupling Mechanism of the Mononuclear Radical Complex [1-N-methyl-1,10-phenanthrolium][Ni(dmit)_2]

The mononuclear radical anionic complex [1-N-methyl-1,10-phenanthrolium][Ni(dmit)_2](dmit = 1,3-dithiole-2-thione-4,5-dithiolate) with a new countercation has been prepared and its crystal structure was determined by X-ray crystallography at 298 and 80 K. In the mononuclear radical anionic complex, the nickel ion assumes a slightly distorted square-planar geometry. There are two and three kinds of intermolecular interactions between adjacent mononuclear radical anionic complexes in the crystal at 298 and 80 K, respectively(i.e., Models A and B at 298 K; and Models C, D and E at 80 K). The variable-temperature magnetic moments indicate a strong antiferromagnetic interaction between the adjacent mononuclear radical anionic complexes, and the theoretical calculations reveal that the stronger antiferromagnetic coupling strength at lower temperature should be contributed to the larger overlap integrals between the short contact atoms. This study is the first to reveal the mechanism of stronger magnetic coupling strength at lower temperature for a mononuclear radical anionic nickel complex with dmit as the ligand.     

Titanocene complexes of the N-methyl and N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolates and 4,5-diselenolate ligands

Cp₂Ti(dithiolene) and Cp₂Ti(diselenolene) complexes containing the N-methyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Me-thiazdt), the N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Ph-thiazdt) and the N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate ligand (Me-thiazds) have been synthesized. Three approaches have been developed in order to generate the dithiolene or the diselenolene ligands which were reacted with Cp₂TiCl₂ to form the corresponding heteroleptic complexes. Their X-ray crystal structures, UV-Vis absorption spectra as well as their redox properties, determined by cyclic voltammetry have been investigated and discussed. Variable-temperature ¹H NMR experiments have been performed in order to determine the activation energies of the chelate ring inversion.     

Structural phase transition of magnetic [Ni(dmit)2]- salts induced by supramolecular cation structures of (M+)([12]crown-4)2

Sandwich-type supramolecular cation structures of (M(+))([12]crown-4)(2) complexes (M(+) = Li(+), Na(+), K(+), and Rb(+)) were introduced as countercations to the [Ni(dmit)(2)](-) anion, which bears an S = (1)/(2) spin, to form novel magnetic crystals (dmit(2-) = 2-thione-1,3-dithiole-4,5-dithiolate). The zigzag arrangement of Li(+)([12]crown-4)(2) cations in Li(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salt induced weak intermolecular interactions of [Ni(dmit)(2)](-) dimers, whose magnetic spins were isolated from each other. The molecular arrangements of cations and anions in M(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salts (M(+) = Na(+), K(+), and Rb(+)) were isostructural to each other. In the case of Na(+)([12]crown-4)(2)[Ni(dmit)(2)](-), the space group C2/m changed to C2/c with a lowering in temperature from 298 to 100 K. This structural change occurred at 222.5 K as a first-order phase transition. The space group C2/m (T = 298 K) in the salt K(+)([12]crown-4)(2)[Ni(dmit)(2)](-) also changed to C2/c (T = 100 K), which transition occurred at 270 K. Crystal structural analyses at 298 and 100 K revealed changes in both supramolecular cation conformation and [Ni(dmit)(2)](-) anion arrangements. The transition from C2/m to C2/c crystals generated a dipole moment in the Na(+)([12]crown-4)(2) and K(+)([12]crown-4)(2) structures, which were reconstructed to cancel the net dipole moment of the C2/c crystals. These cation transformations led to changes in intermolecular interactions between the [Ni(dmit)(2)](-) anions via structural rearrangements. The crystal structure of C2/c was stabilized in Rb(+)([12]crown-4)(2)[Ni(dmit)(2)](-) at 298 K. The [Ni(dmit)(2)](-) configuration in these salts with the C2/c space group was a one-dimensional uniform chain, which showed the temperature-dependent magnetic susceptibility of a one-dimensional linear Heisenberg antiferromagnetic chain.     

CpNi(diselenolene)] neutral radical complexes: electron paramagnetic resonance and density functional theory investigations

77Se-enriched CpNi(bds) (bds = 1,2-benzenediselenolate), has been synthesized and its g tensor and 77Se hyperfine tensors have been obtained from its frozen solution electron paramagnetic resonance (EPR) spectrum. These parameters are consistent with those calculated by density functional theory (DFT); it is shown that 10% of the spin is localized on each selenium and that the direction associated to the maximum 77Se couplings is aligned along the gmin direction, perpendicular to the Ni(bds) plane. EPR measurements and DFT calculations are also carried out on the 77Se enriched complex CpNi(dsit) as well on the two dithiolene analogues CpNi(bdt) and CpNi(dmit). The optimized structures of the isolated CpNi(bds) and CpNi(bdt) complexes have been used to generate the idealized dimers (bds)NiCp...CpNi(bds) and (bdt)NiCp...CpNi(bdt) characterized by Cp...Cp overlap. The exchange parameters J calculated at the DFT level for these systems are in reasonable accord with the experimental values. The influence of the geometry of the dimer on its magnetic properties is assessed by calculating the variation of J as a function of the relative orientation of the two Ni(diselenolene) or Ni(dithiolene) planes.     

Crystal structure and magnetic properties of Gd2([18]crown-6)2(OH)2(CH3CN)2[Ni(dmit)2]4 complex having f- and pi-spins

Crystal structure and magnetic properties of Gd(2)([18]crown-6)(2)(OH)(2)(CH(3)CN)(2)[Ni(dmit)(2)](2) (dmit(2)(-) = 2-thioxo-1,3-dithiole-4,5-dithiolate) are reported. Gd(3+) ions (S = (7)/(2)) were introduced into the pi-spin network of [Ni(dmit)(2)](-) (S = (1)/(2)) complex as a binuclear supramolecular cation, Gd(2)([18]crown-6)(2)(OH)(2)(CH(3)CN)(2), in which two Gd([18]crown-6) units are bridged with two hydroxide ions. The weak antiferromagnetic interactions between Gd.Gd through hydroxide ions were observed, and [Ni(dmit)(2)](-) formed isolated monomers and dimers in the crystal.     

Electrical properties and electronic states of molecular conductors based on unsymmetrical organometallic-dithiolene gold(III) complexes

The electronic properties of cation radical salts derived from organometallic mixed-ligand complexes [(ppy)Au(S-S)](ppy- = C-dehydro-2-phenylpyridine(-); S-S(2-) = dithiolene ligand) with Au(III)-C sigma-bond were investigated. A 2:1 salt complex [(ppy)Au(C8H4S8)]2[PF6] (C8H4S8(2-) = 2-((4,5-ethylenedithio)-1,3-dithiole-2-ylidene)-1,3-dithiole-4,5-dithiolate(2-)) exhibited semiconductive behavior under ambient pressure (rho rt = 2.6 Omega cm, Ea = 0.03 eV). Magnetic measurements show that it is a Mott insulator close to the metal-insulator boundary. Raman and infrared spectra have revealed that the complex has a quasi-one-dimensional dimeric structure consisting of uniformly charged donor molecules. The complex exhibits metallic behavior at pressures above 0.8 GPa. In contrast, a similar compound [(ppy)Au(C8H4S6O2)]2[BF4] (C8H4S6O2(2-) = 2-((4,5-ethylenedioxy)-1,3-dithiole-2-ylidene)-1,3-dithiole-4,5-dithiolate(2-)) is a band insulator.     

Synthesis and Structural Characterization of the Complex 〔Et_4N〕_2〔Ni_2(C_2S_4)(C_3S_5)_2〕

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