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1.
Mono‐ and multinuclear complexes of ruthenium and [n]cycloparaphenylene (CPP, n=5 and 6) were synthesized in excellent yields through ligand exchange of the cationic complex [(Cp)Ru(CH3CN)3](PF6) with CPP. In the multinuclear complexes, ruthenium selectively coordinated to alternate paraphenylene units to give bis‐ and tris‐coordinated Ru complexes for [5] and [6]CPPs, respectively. Single‐crystal X‐ray analysis revealed the Ru was coordinated with η6‐hapticity on the convex surface of CPP.  相似文献   

2.
Reaction of α-amino acids (HL) with [Ru(PPh3)3Cl2] in the presence of a base afforded a family of complexes of type [Ru(PPh3)2(L)2]. These complexes are diamagnetic (low-spin d6, S=0) and show ligand-field transitions in the visible region. 1H and 31P NMR spectra of the complexes indicate the presence of C2 symmetry. Cyclic voltammetry on the [Ru(PPh3)2(L)2] complexes show a reversible ruthenium(II)–ruthenium(III) oxidation in the range 0.30–0.42 V vs. SCE. An irreversible ruthenium(III)–ruthenium(IV) oxidation is also displayed by two complexes near 1.5 V vs. SCE.  相似文献   

3.
It has been shown that ruthenium can be determined in solutions of ammonium nitrosopentachlororuthenate (NH4)2[Ru(NO)Cl5] with nitroso and aquachloro complexes present simultaneously by its reaction with 1,10-phenanthroline and in solutions of sulfate complexes using microwave radiation. It is found by molecular absorption and luminescence studies that the composition of the complex formed corresponds to ruthenium(II) tris-(1,10-phenanthrolinate) {[Ru(Phen)3]2+}. The complexation time is decreased by several tens of times (down to 5 min) compared to conventional heating, and a 100% yield of the complex is achieved. In the presence of HCl, the conversion of nitroso species to aquachloro ruthenium complexes upon microwave irradiation is inefficient. It is found that, compared to [Ru2OCl10]4–, [Ru(NO)Cl5]2– is more labile in the complexation reactions of ruthenium with 1,10-phenanthroline under microwave irradiation. Regardless of the concentration of H2SO4 (1.7–12 M) in the starting solutions, ruthenium sulfate complexes can be converted in a microwave field to more labile chloride complexes.  相似文献   

4.
Treatment of [Ru(PPh3)3Cl2] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl3(κ2-N,N-NH2CH2CH2NMe2)(PPh3)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh3)3], [Ru(CO)2Cl2] or [Ru(tht)4Cl2] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ3-N,N,O-L)(CO)(PPh3)] (2), [RuCl(κ3-N,N,O-L)(CO)2] (3), and a ruthenium(III) complex [RuCl2(κ3-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH2Cl2, 2·CH2Cl2, 3 and 4 have been determined by single-crystal X-ray diffraction.  相似文献   

5.
Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido‐[(Cp*Ru)2B3H9] ( 1 ) with other ligand systems was explored. In this regard, mild thermolysis of nido‐ 1 with 2‐mercaptobenzothiazole (2‐mbzt), 2‐mercaptobenzoxazole (2‐mbzo) and 2‐mercaptobenzimidazole (2‐mbzi) ligands were performed which led to the isolation of bis(sigma)borate complexes [Cp*RuBH3L] ( 2 a – c ) and β‐agostic complexes [Cp*RuBH2L2] ( 3 a – c ; 2 a , 3 a : L=C7H4NS2; 2 b , 3 b : L=C7H4NSO; 2 c , 3 c : L=C7H5N2S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3 a with [PPh2(CH2)nPPh2] (n=1–3) yielded [Cp*Ru(PPh2(CH2)nPPh2)‐BH2(L2)] ( 4 a – c ; 4 a : n=1; 4 b : n=2; 4 c : n=3; L=C7H4NS2). Mild thermolysis of 2 a with [PPh2(CH2)nPPh2] (n=1–3) led to the isolation of [Cp*Ru(PPh2(CH2)nPPh2)(L)] (L=C7H4NS2 5 a – c ; 5 a : n=1; 5 b : n=2; 5 c : n=3). Treatment of 4 a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [Cp*Ru(R?C?CH2)BH(L2)] ( 6 and 7 ; 6 : R=Ph; 7 : R=COOCH3; L=C7H4NS2). Complexes 6 and 7 can also be viewed as η‐alkene complexes of ruthenium that feature a dative bond to the ruthenium centre from the vinylinic double bond. In addition, DFT computations were performed to shed light on the bonding and electronic structures of the new compounds.  相似文献   

6.
This work describes the preparation and characterisation of ruthenium(II) complexes of several ONS donor ligands in the form of ring-substituted 4-phenylthiosemicarbazones of salicylaldehyde and o-hydroxyacetophenone. Reactions of these thiosemicarbazone ligands with [Ru(PPh3)3]Cl2 in refluxing MeOH furnished ruthenium(II) complexes of general formula [Ru(PPh3)2(LH)Cl] where the ligands acted as monoanionic tridentate ONS donors attached to the ruthenium(II) acceptor centre through the deprotonated phenolic oxygen, thione sulphur and azomethine nitrogen.  相似文献   

7.
Cationic [Ru(η5-C5H5)(CH3CN)3]+ complex, tris(acetonitrile)(cyclopentadienyl)ruthenium(II), gives rise to a very rich organometallic chemistry. Combined with diimine ligands, and 1,10-phenanthroline in particular, this system efficiently catalyzes diazo decomposition processes to generate metal-carbenes which undergo a series of original transformations in the presence of Lewis basic substrates. Herein, syntheses and characterizations of [CpRu(Phen)(L)] complexes with (large) lipophilic non-coordinating (PF6 and BArF) and coordinating TRISPHAT-N anions are reported. Complex [CpRu(η6-naphthalene)][BArF] ( [1][BArF] ) is readily accessible, in high yield, by direct counterion exchange between [1][PF6] and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF) salts. Ligand exchange of [1][BArF] in acetonitrile generated stable [Ru(η5-C5H5)(CH3CN)3][BArF] ( [2][BArF] ) complex in high yield. Then, the desired [CpRu(Phen)(CH3CN)] ( [3] ) complexes were obtained from either the [1] or [2] complex in the presence of the 1,10-phenanthroline as ligand. For characterization and comparison purposes, the anionic hemilabile ligand TRISPHAT−N (TTN) was introduced on the ruthenium center, from the complex [3][PF6] , to quantitatively generate the desired complex [CpRu(Phen)(TTN)] ( [4] ) by displacement of the remaining acetonitrile ligand and of the PF6 anion. Solid state structures of complexes [1][BArF] , [2][BArF] , [3][BArF] , [3][PF6] and [4] were determined by X-ray diffraction studies and are discussed herein.  相似文献   

8.
Reaction of [Ru(η6p‐cymene)Cl2]2 with two equivalents of [Ph4P][Cl] in CH2Cl2 yields [Ph4P][Ru(η6p‐cymene)Cl3], containing a trichlororuthenate(II) anion. In solution, an equilibrium between the product and [Ru(η6p‐cymene)Cl2]2 is observed, which in CDCl3 is nearly completely shifted to the dimer, whereas in CD2Cl2 essentially a 1:1‐mixture of the two ruthenium species is present. Crystallization from CH2Cl2/pentane yielded two different crystals, which were identified by X‐ray analysis as [Ph4P][Ru(η6p‐cymene)Cl3] and [Ph4P][Ru(η6p‐cymene)Cl3]·CH2Cl2.  相似文献   

9.
The reactions of mono‐ and bidentate aromatic nitrogen‐containing ligands with [Ru(CO)3Cl2]2 in alcohols have been studied. In alcoholic media the nitrogen ligands act as bases promoting acidic behaviour of alcohols and the formation of alkoxy carbonyls [Ru(N–N)(CO)2Cl(COOR)] and [Ru(N)2(CO)2Cl(COOR)]. Other products are monomers of type [Ru(N)(CO)3Cl2], bridged complexes such as [Ru(CO)3Cl2]2(N), and ion pairs of the type [Ru(CO)3Cl3]? [Ru(N–N)(CO)3Cl]+ (N–N = chelating aromatic nitrogen ligand, N = non‐chelating or bridging ligand). The reaction and the product distribution can be controlled by adjusting the reaction stoichiometry. The reactivity of the new ruthenium complexes was tested in 1‐hexene hydroformylation. The activity can be associated with the degree of stability of the complexes and the ruthenium–ligand interaction. Chelating or bridging nitrogen ligands suppresses the activity strongly compared with the bare ruthenium carbonyl chloride, while the decrease in activity is less pronounced with monodentate ligands. A plausible catalytic cycle is proposed and discussed in terms of ligand–ruthenium interactions. The reactivity of the ligands as well as the catalytic cycle was studied in detail using the computational DFT methods. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

10.
A series of ruthenium alkenylacetylide complexes trans-[Ru{C≡CC(=CH2)R}Cl(dppe)2] (R=Ph ( 1 a ), cC4H3S ( 1 b ), 4-MeS-C6H4 ( 1 c ), 3,3-dimethyl-2,3-dihydrobenzo[b]thiophene (DMBT) ( 1 d )) or trans-[Ru{C≡C-cC6H9}Cl(dppe)2] ( 1 e ) were allowed to react with the corresponding propargylic alcohol HC≡CC(Me)R(OH) (R=Ph ( A ), cC4H3S ( B ), 4-MeS-C6H4 ( C ), DMBT ( D ) or HC≡C-cC6H10(OH) ( E ) in the presence of TlBF4 and DBU to presumably give alkenylacetylide/allenylidene intermediates trans-[Ru{C≡CC(=CH2)R}{C=C=C(Me)}(dppe)2]PF6 ([ 2 ]PF6). These complexes were not isolated but deprotonated to give the isolable bis(alkenylacetylide) complexes trans-[Ru{C≡CC(=CH2)R}2(dppe)2] (R=Ph ( 3 a ), cC4H3S ( 3 b ), 4-MeS-C6H4 ( 3 c ), DMBT ( 3 d )) and trans-[Ru{C≡C-cC6H9}2(dppe)2] ( 3 e ). Analogous reactions of trans-[Ru(CH3)2(dmpe)2], featuring the more electron-donating 1,2-bis(dimethylphosphino)ethane (dmpe) ancillary ligands, with the propargylic alcohols A or C and NH4PF6 in methanol allowed isolation of the intermediate mixed alkenylacetylide/allenylidene complexes trans-[Ru{C≡CC(=CH2)R}{C=C=C(Me)}(dmpe)2]PF6 (R=Ph ([ 4 a ]PF6), 4-MeS-C6H4 ([ 4 c ]PF6). Deprotonation of [ 4 a ]PF6 or [ 4 c ]PF6 gave the symmetric bis(alkenylacetylide) complexes trans-[Ru{C≡CC(=CH2)R}2(dmpe)2] (R=Ph ( 5 a ), 4-MeS-C6H4 ( 5 c )), the first of their kind containing the dmpe ancillary ligand sphere. Attempts to isolate bis(allenylidene) complexes [Ru{C=C=C(Me)R}2(PP)2]2+ (PP=dppe, dmpe) from treatment of the bis(alkenylacetylide) species 3 or 5 with HBF4 ⋅ Et2O were ultimately unsuccessful.  相似文献   

11.
Ruthenium polypyridyl complexes are widely used as light harvesters in dye‐sensitized solar cells. Since one of the potential applications of single‐wall carbon nanotubes (SWCNTs) and their derived materials is their use as active components in organic and hybrid solar cells, the study of the photochemistry of SWCNTs with tethered ruthenium polypyridyl complexes is important. A water‐soluble ruthenium tris(bipyridyl) complex linked through peptidic bonds to SWCNTs (Ru‐SWCNTs) was prepared by radical addition of thiol‐terminated SWCNT to a terminal C?C double bond of a bipyridyl ligand of the ruthenium tris(bipyridyl) complex. The resulting macromolecular Ru‐SWCNT (≈500 nm, 15.6 % ruthenium complex content) was water‐soluble and was characterized by using TEM, thermogravimetric analysis, chemical analysis, and optical spectroscopy. The emission of Ru‐SWCNT is 1.6 times weaker than that of a mixture of [Ru(bpy)3]2+ and SWCNT of similar concentration. Time‐resolved absorption optical spectroscopy allows the detection of the [Ru(bpy)3]2+‐excited triplet and [Ru(bpy)3]+. The laser flash studies reveal that Ru‐SWCNT exhibits an unprecedented two‐photon process that is enabled by the semiconducting properties of the SWCNT. Thus, the effect of the excitation wavelength and laser power on the transient spectra indicate that upon excitation of two [Ru(bpy)3]2+ complexes of Ru‐SWCNT, a disproportionation process occurs leading to delayed formation of [Ru(bpy)3]+ and the performance of the SWCNT as a semiconductor. This two‐photon delayed [Ru(bpy)3]+ generation is not observed in the photolysis of [Ru(bpy)3]3+; SWCNT acts as an electron wire or electron relay in the disproportionation of two [Ru(bpy)3]2+ triplets in a process that illustrates that the SWCNT plays a key role in the process. We propose a mechanism for this two‐photon disproportionation compatible with i) the need for high laser flux, ii) the long lifetime of the [Ru(bpy)3]2+ triplets, iii) the semiconducting properties of the SWNT, and iv) the energy of the HOMO/LUMO levels involved.  相似文献   

12.
Polypyridyl ruthenium(II) dicarbonyl complexes with an N,O- and/or N,N-donor ligand, [Ru(pic)(CO)2Cl2] (1), [Ru(bpy)(pic)(CO)2]+ (2), [Ru(pic)2(CO)2] (3), and [Ru(bpy)2(CO)2]2+ (4) (pic=2-pyridylcarboxylato, bpy=2,2′-bipyridine) were prepared for comparison of the electron donor ability of these ligands to the ruthenium center. A carbonyl group of [Ru(L1)(L2)(CO)2]n (L1, L2=bpy, pic) successively reacted with one and two equivalents of OH to form [Ru(L1)(L2)(CO)(C(O)OH)]n−1 and [Ru(L1)(L2)(CO)(CO2)]n−2. These three complexes exist as equilbrium mixtures in aqueous solutions and the equilibrium constants were determined potentiometrically. Electrochemical reduction of 2 in CO2-saturated CH3CN–H2O at −1.5 V selectively produced CO.  相似文献   

13.
The ruthenium(II) complex fac-[Ru(CO)2(H2O)3(C(O)C2H5)][CF3SO3] dissolved in aqueous tetrabutylammonium hydrogensulfate ([(CH3(CH2)3)4N][HSO4]) or sodium hydrogensulfate (NaHSO4) catalyzes the hydrocarboxylation of ethylene to propionic acid and additionally produces minor amounts of hydrocarbonylation products (diethyl ketone and propanal), under water-gas shift reaction conditions. This system is stable with a selectivity of 90% to propionic acid for high ethylene conversion. A turnover frequency of propionic acid, TOF(C2H5CO2H)/24?h?=?5?×?103 (TOF (C2H5CO2H)?=?([(moles of C2H5CO2H)/(moles of Ru)?×?rt)]?×?24?h) was achieved for Ru?=?7.45?×?10?4?mol, [(CH3(CH2)3)4N][HSO4]?=?80?g (2.36?×?10?2?mol); H2O?=?40?g (2.22?mol); CO?=?C2H4?=?20?g (total pressure?=?88?atm); T?=?150°C by a reaction time (rt) of 2.87?h. The countercation (sodium or tetrabutylammonium), the ruthenium concentration and the hydrogensulfate/H2O ratio of the medium affect the catalytic reaction. A nonlinear dependence on total ruthenium concentration was shown. The data are discussed in terms of a potential catalytic cycle. Formation of propionic acid comes from hydrolysis, and formation of diethyl ketone and propanal comes from hydrogenolysis of the Ru-ketyl and Ru-acyl complexes, respectively.  相似文献   

14.
Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation‐resistant and can stabilize high‐oxidation‐state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2]2+ (qpy=2,2′:6′,2′′:6′′,2′′′‐quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze CeIV‐driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy‐N,N′′′‐dioxide (ONNO) complexes [Ru(ONNO)(L)2]3+ which are the real catalysts for water oxidation.  相似文献   

15.
Spectral-kinetic luminescence characteristics of the complexes cis-[Ru(bpy)(dppe)X2], cis- [Ru(bpy)2(PPh3)X](BF4) and cis-[Ru(bpy)2X2] [bpy = 2,2'-bipyridyl, dppe = 1,2-bis(diphenylphosphino)ethane, PPh3 is triphenylphosphine, X = NO2 - and CN-] in the ethanol-methanol 4:1 mixtures and adsorbed on the oxide SiO2 or porous polyacrylonitrile polymer surface were studied. Luminescence and luminescence exitation spectra were registered at 77 and 293 K in 230-750 nm range and the luminescence decay time was measured. Introduction of phosphine ligands to the ruthenium(II) bipyridyl complexes inner sphere leads to rise in singlet and triplet state energy at the charge transfer from Ru(II) to 2,2'-bipyridyl in the series [Ru(bpy)2X2] < Ru(bpy)2(PPh3)X](BF4) < [Ru(bpy)(dppe)X2]. The complex adsorption on SiO2 or polyacrylonitrile surface affects noticeably the luminescence spectro-kinetic characteristics.  相似文献   

16.
Monocyclopentadienyl titanium imidazolin‐2‐iminato complexes [Cp′Ti(L)X2] 1a (Cp′ = cyclopentadienyl, L = 1,3‐di‐tert‐butylimidazolin‐2‐imide, X = Cl), 1b (X = CH3); 2 (Cp′ = cyclopentadienyl, L = 1,3‐diisopropylimidazolin‐2‐imide, X = Cl); 3 (Cp′ = tert‐butylcyclopentadienyl, L = 1,3‐di‐tert‐butylimidazolin‐2‐imide, X = Cl), upon activation with methylaluminoxane (MAO) were active for the polymerization of ethylene and propylene and the copolymerization of ethylene and 1‐hexene. Catalysts derived from imidazolin‐2‐iminato tropidinyl titanium complex 4 = [(Trop)Ti(L)Cl2] (Trop = tropidinyl, L = 1,3‐di‐tert‐butylimidazolin‐2‐imide) were much less active. Narrow polydispersities were observed for ethylene and propylene polymerization, but the copolymerization of ethylene/hexene led to bimodal molecular weight distributions. The productivity of catalysts derived from the dialkyl complex 1b activated with [Ph3C][B(C6F5)4] or B(C6F5)3 were less active for ethylene/hexene copolymerization but yielded ethylene/hexene copolymers of narrower molecular weight distributions than those derived from 1a/MAO. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6064–6070, 2008  相似文献   

17.
A new series of monoselenoquinone and diselenoquinone π complexes, [(η6p‐cymene)Ru(η4‐C6R4SeE)] (R=H, E=Se ( 6 ); R=CH3, E=Se ( 7 ); R=H, E=O ( 8 )), as well as selenolate π complexes [(η6p‐cymene)Ru(η5‐C6H3R2Se)][SbF6] (R=H ( 9 ); R=CH3 ( 10 )), stabilized by arene ruthenium moieties were prepared in good yields through nucleophilic substitution reactions from dichlorinated‐arene and hydroxymonochlorinated‐arene ruthenium complexes [(η6p‐cymene)Ru(C6R4XCl)][SbF6]2 (R=H, X=Cl ( 1 ); R=CH3, X=Cl ( 2 ); R=H, X=OH ( 3 )) as well as the monochlorinated π complexes [(η6p‐cymene)Ru(η5‐C6H3R2Cl)][SbF6]2 (R=H ( 4 ); R=CH3 ( 5 )). The X‐ray crystallographic structures of two of the compounds, [(η6p‐cymene)Ru(η4‐C6Me4Se2)] ( 7 ) and [(η6p‐cymene)Ru(η4‐C6H4SeO)] ( 8 ), were determined. The structures confirm the identity of the target compounds and ascertain the coordination mode of these unprecedented ruthenium π complexes of selenoquinones. Furthermore, these new compounds display relevant cytotoxic properties towards human ovarian cancer cells.  相似文献   

18.
Ruthenium(III) complexes formulated as K2[Ru(sar)Cl4]·H2O and K[Ru(dmgly)2Cl2]·3H2O containing bidentate chelates N-methylglycine (sarcosine, sar) or N,N-dimethylglycine (dmgly) as well as K[Ru(pdda)Cl2]·2.5H2O complex with tetradentate 1,3-propylenediamine-N,N′-diacetato were synthesized. The complexes were obtained by direct reaction of ruthenium(III) chloride with the corresponding bidentate or tetradentate ligand followed by addition of a base (KOH). These new complexes were characterized by elemental analysis, IR and electronic absorption spectroscopy. To assess selectivity in the antitumor action of these complexes, their antiproliferative activities against human adenocarcinoma HeLa cells, human myelogenous leukemia K562 cells, human breast carcinoma MDA-MB-361 and MDA-MB-453 cells and normal immunocompetent PBM cells were determined.  相似文献   

19.
Ruthenium(II) polypyridyl complexes with macromolecular ligands poly(methylolacrylamide-co-vinylpyridine) and poly (acrylamide-co-vinylpyridine) have been synthesized. The macromolecular ruthenium (II) complexes which are soluble in water have been characterized and their absorption and emission properties have been studied in aqueous solution. Photolysis of the complex in aqueous solution leads to photoaquation reactions with release of coordinated pyridines of the polymer. In the case of monomeric complex, cis-[Ru(bpy)2(py)2]Cl2, photolysis in water in presence of Cl? ions produces only the substitution of the pyridine by water whereas in the polymeric complexes, [Ru(bpy)2(MAAM-co-VP)2]Cl2 photolysis in the presence of chloride produces [Ru(bpy)2(MAAM-co-VP)Cl]Cl and [Ru(bpy)2(AM-co-VP)Cl]Cl, respectively. Quantum yields for the photosubstitution reactions have been determined and mechanistic details are outlined.  相似文献   

20.
A new bimetallic complex, [Ru(biq)2(dpp)PtCl2](PF6)2 (where biq = 2,2′-biquinoline and dpp = 2,3-bis(2-pyridyl)pyrazine), containing a cis-PtCl2 moiety coupled to a sterically strained Ru(II)-based chromophore was designed, synthesized, and investigated with respect to its spectroscopic, redox, photo-induced ligand exchange, and DNA-interaction properties. The electrochemistry of the designed complex was found to be consistent with the bridging coordination of the dpp ligand and formation of the bimetallic complex. The complex displays intense ligand-based π → π* transitions in the UV region and metal-to-ligand charge-transfer transitions (MLCT) in the visible region. The loss of bridging coordination of the dpp ligand and formation of complexes, [Ru(biq)2(CH3CN)2]2+ and [Pt(dpp)(CH3CN)2]2+ was observed when an acetonitrile solution of the metal complex was irradiated with visible light (λirr ≥ 550 nm). The designed complex displays covalent binding with DNA in dark through the cis-PtCl2 moiety, as confirmed by agarose gel electrophoresis. Upon photoirradiation, the complex dissociates into two DNA-binding moieties and displays covalent binding through: (i) a cis-PtL2 subunit of [Ptdpp(L)2]2+ and (ii) open coordination sites of the ruthenium of [Ru(biq)2(L)2]2+ (L = solvent). The designed complex represents the first Ru(II)Pt(II) complex that undergoes photo-induced ligand exchange and displays multifunctional interactions with DNA upon photoirradiation.  相似文献   

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