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1.
Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous complex, [2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl-κ2P,P′](2-phenylpyridine-κN)copper(I) hexafluoridophosphate, rac-[Cu(C44H32P2)(C11H9N)]PF6, conventionally abbreviated rac-[Cu(BINAP)(2-PhPy)]PF6 ( I ), where BINAP and 2-PhPy represent 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl and 2-phenylpyridine, respectively, is described. In this complex, the asymmetric unit consists of a hexafluoridophosphate anion and a heteroleptic cuprous complex cation, in which the cuprous centre in a CuP2N coordination triangle is coordinated by two P atoms from the BINAP ligand and by one N atom from the 2-PhPy ligand. Time-dependent density functional theory (TD–DFT) calculations show that the UV–Vis absorption of I should be attributed to ligand-to-ligand charge transfer (LLCT) characteristic excited states. It was also found that the paper-based film of this complex exhibited obvious luminescence light-up sensing for pyridine.  相似文献   

2.
In the title heteroleptic cuprous complex, (acetonitrile‐κN)({2‐[2‐(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane‐κ2P,P′)[2‐(pyridin‐4‐yl‐κN)‐1,3‐benzoxazole]copper(I) hexafluoridophosphate, [Cu(C36H28OP2)(CH3CN)(C12H8N2O)]PF6, conventionally abbreviated [Cu(POP)(CH3CN)(4‐PBO)]PF6, where POP is the diphosphane ligand {2‐[2‐(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane and 4‐PBO is the N‐containing ligand 2‐(pyridin‐4‐yl)‐1,3‐benzoxazole, the asymmetric unit consists of a hexafluoridophosphate anion and a whole mononuclear cation, where the CuI centre is coordinated by two P atoms from the POP ligand, by one N atom from the 4‐PBO ligand and by the N atom of the coordinated acetonitrile molecule, giving rise to a CuP2N2 distorted tetrahedral coordination geometry. The electronic absorption, photoluminescence and thermal stability properties of this complex have been studied on as‐synthesized samples, which had previously been examined by powder X‐ray diffraction. A yellow emission signal is attributed to an excited state arising from metal‐to‐ligand charge transfer (MLCT).  相似文献   

3.
Although there are many examples of acetate complexes, acetamide complexes are virtually unknown. A side‐by‐side comparison in (acetato‐κ2O,O′)(1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane‐κ4N)nickel(II) hexafluoridophosphate, [Ni(C2H3O2)(C12H28N4)]PF6, (1), and (acetamidato‐κ2O,O′)(1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane‐κ4N)nickel(II) hexafluoridophosphate, [Ni(C2H4NO)(C12H28N4)]PF6, (2), shows the steric equivalence between these two ligands, suggesting that acetamide could be considered as a viable acetate replacement for electronic tuning.  相似文献   

4.
The structure of catena‐poly[[{bis[4‐(trimethylammonio)benzenethiolate‐κS]mercury(II)}‐μ‐1,1′‐(ethane‐1,2‐diyl)bis(1H‐benzimidazole)‐κ2N3:N3′] bis(hexafluoridophosphate) 0.25‐hydrate], {[Hg(C16H14N4)(C9H13NS)2](PF6)2·0.25H2O}n, contains a one‐dimensional zigzag chain. The HgII cation is coordinated by two S atoms of two 4‐(trimethylammonio)benzenethiolate (Tab) ligands and by two N atoms from two different 1,1′‐(ethane‐1,2‐diyl)bis(1H‐benzimidazole) ligands, forming a distorted seesaw‐shaped coordination geometry. The F atoms of the hexafluoridophosphate anion interact with the H atoms of the Tab ligand, generating a two‐dimensional network. Furthermore, this layer is connected to neighbouring layers via H...π interactions, thereby forming a three‐dimensional hydrogen‐bonded structure. In catena‐poly[[{[4‐(trimethylammonio)benzenethiolate‐κS]mercury(II)}bis[μ‐4‐(trimethylammonio)benzenethiolate‐κ2S:S]{[4‐(trimethylammonio)benzenethiolate‐κS]mercury(II)}‐μ‐1,1′‐(hexane‐1,6‐diyl)bis(1H‐benzimidazole)‐κ2N3:N3′] tetrakis(hexafluoridophosphate)], {[Hg2(C20H22N4)(C9H13NS)4](PF6)4}n, each HgII cation is coordinated by two S atoms of two Tab ligands and one N atom of the 1,1′‐(hexane‐1,6‐diyl)bis(1H‐benzimidazole) (hbbm) ligand, forming a distorted T‐shaped coordination geometry, while longer secondary Hg...S bonds join two such units across a centre of inversion to give the tetravalent cation. Adjacent {[Hg(Tab)2]2(μ‐hbbm)}4+ cations are linked through the centrosymmetric hbbm ligands to afford a one‐dimensional chain extending along the b axis. Several F atoms interact with the H atoms of the Tab and hbbm ligands, while the S atom interacts with an aromatic H atom of a different Tab ligand, to afford a complex intra‐ and intermolecular hydrogen‐bonding arrangement in a three‐dimensional structure.  相似文献   

5.
The title di­phenyl­carbene porphyrin complex (di­phenyl­carbenyl‐κC)(methanol‐κO)(5,10,15,20‐tetra‐p‐tolyl­por­phy­rin­ato‐κ4N)ruthenium(II) methanol solvate, [Ru­(C13H10)(C48H36N4)(CH4O)]·CH4O, has a six‐coordinate Ru atom with a methanol mol­ecule as the second axial ligand. The carbene fragment is slightly distorted from an ideal sp2 configuration, with a C(phenyl)—C(carbene)—C(phenyl) angle of 112.2 (3)°. The Ru—C bond length of 1.845 (3) Å is comparable with other carbene complexes. The two phenyl rings of the carbene ligand are perpendicular to the carbene plane. Methanol solvate mol­ecules link the methanol ligands of adjacent porphyrin complexes via hydrogen bonds.  相似文献   

6.
The reaction of [FeL(MeOH)2] {where L is the tetradentate N2O2‐coordinating Schiff base‐like ligand (E,E)‐diethyl 2,2′‐[1,2‐phenylenebis(nitrilomethylidyne)]bis(3‐oxobutanoate)(2−) and MeOH is methanol} with 3‐aminopyridine (3‐apy) in methanol results in the formation of the octahedral complex (3‐aminopyridine‐κN1){(E,E)‐diethyl 2,2′‐[1,2‐phenylenebis(nitrilomethylidyne)]bis(3‐oxobutanoato)(2−)‐κ4O3,N,N′,O3′}(methanol‐κO)iron(II), [Fe(C20H22N2O6)(C5H6N2)(CH4O)] or [FeL(3‐apy)(MeOH)], in which the FeII ion is centered in an N3O3 coordination environment with two different axial ligands. This is the first example of an octahedral complex of this multidentate ligand type with two different axial ligands, and the title compound can be considered as a precursor for a new class of complexes with potential spin‐crossover behavior. An infinite two‐dimensional hydrogen‐bond network is formed, involving the amine NH group, the methanol OH group and the carbonyl O atoms of the equatorial ligand. T‐dependent susceptibility measurements revealed that the complex remains in the high‐spin state over the entire temperature range investigated.  相似文献   

7.
The reaction of NiCl2 with 1,3‐bis[(diphenylphosphanyl)methyl]hexahydropyrimidine in the presence of 2,6‐dimethylphenyl isocyanide and KPF6 afforded a new pentacoordinated PCP pincer NiII complex, namely {1,3‐bis[(diphenylphosphanyl)methyl]hexahydropyrimidin‐2‐yl‐κN2}(2,6‐dimethylphenyl isocyanide‐κC)nickel(II) hexafluoridophosphate 0.70‐hydrate, [Ni(C9H9N)(C30H30ClN2P2)]PF6·0.7H2O or [NiCl{C(NCH2PPh2)2(CH2)3‐κ3P,C,P′}(Xylyl‐NC)]PF6·0.7H2O, in very good yield. Its X‐ray structure showed a distorted square‐pyramidal geometry and the compound does not undergo dissociation in solution, as shown by variable‐temperature NMR and UV–Vis studies. Density functional theory (DFT) calculations provided an insight into the bonding; the nickel dsp2‐hybridized orbitals form the basal plane and the nearly pure p orbital forms the axial bond. This is consistent with the NBO (natural bond orbital) analysis of analogous nickel(II) complexes.  相似文献   

8.
Iron is of interest as a catalyst because of its established use in the Haber–Bosch process and because of its high abundance and low toxicity. Nitrogen‐heterocyclic carbenes (NHC) are important ligands in homogeneous catalysis and iron–NHC complexes have attracted increasing attention in recent years but still face problems in terms of stability under oxidative conditions. The structure of the iron(II) complex [1,1′‐bis(pyridin‐2‐yl)‐2,2‐bi(1H‐imidazole)‐κN3][3,3′‐bis(pyridin‐2‐yl‐κN)‐1,1′‐methanediylbi(1H‐imidazol‐2‐yl‐κC2)](trimethylphosphane‐κP)iron(II) bis(hexafluoridophosphate), [Fe(C17H14N6)(C16H12N6)(C3H9P)](PF6)2, features coordination by an organic decomposition product of a tetradentate NHC ligand in an axial position. The decomposition product, a C—C‐coupled biimidazole, is trapped by coordination to still‐intact iron(II) complexes. Insights into the structural features of the organic decomposition products might help to improve the stability of oxidation catalysts under harsh conditions.  相似文献   

9.
Two mononuclear copper complexes, {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN2)methyl]amine‐κN}(3,5‐dimethyl‐1H‐pyrazole‐κN2)(perchlorato‐κO)copper(II) perchlorate, [Cu(ClO4)(C5H8N2)(C12H19N5)]ClO4, (I), and {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN2)methyl]amine‐κN}bis(3,5‐dimethyl‐1H‐pyrazole‐κN2)copper(II) bis(hexafluoridophosphate), [Cu(C5H8N2)2(C12H19N5)](PF6)2, (II), have been synthesized by the reactions of different copper salts with the tripodal ligand tris[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (TDPA) in acetone–water solutions at room temperature. Single‐crystal X‐ray diffraction analysis revealed that they contain the new tridentate ligand bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (BDPA), which cannot be obtained by normal organic reactions and has thus been captured in the solid state by in situ synthesis. The coordination of the CuII ion is distorted square pyramidal in (I) and distorted trigonal bipyramidal in (II). The new in situ generated tridentate BDPA ligand can act as a meridional or facial ligand during the process of coordination. The crystal structures of these two compounds are stabilized by classical hydrogen bonding as well as intricate nonclassical hydrogen‐bond interactions.  相似文献   

10.
Luminescent CuI complexes have emerged as promising substitutes for phosphorescent emitters based on Ir, Pt and Os due to their abundance and low cost. The title heteroleptic cuprous complex, [9,9‐dimethyl‐4,5‐bis(diphenylphosphanyl)‐9H‐xanthene‐κ2P ,P ](2‐methylquinolin‐8‐ol‐κ2N ,O )copper(I) hexafluorophosphate, [Cu(C10H9NO)(C39H32OP2)]PF6, conventionally abbreviated as [Cu(Xantphos)(8‐HOXQ)]PF6, where Xantphos is the chelating diphosphine ligand 9,9‐dimethyl‐4,5‐bis(diphenylphosphanyl)‐9H‐xanthene and 8‐HOXQ is the N ,O‐chelating ligand 2‐methylquinolin‐8‐ol that remains protonated at the hydroxy O atom, is described. In this complex, the asymmetric unit consists of a hexafluorophosphate anion and a whole mononuclear cation, where the CuI atom is coordinated by two P atoms from the Xantphos ligand and by the N and O atoms from the 8‐HOXQ ligand, giving rise to a tetrahedral CuP2NO coordination geometry. The electronic absorption and photoluminescence properties of this complex have been studied on as‐synthesized samples, whose purity had been determined by powder X‐ray diffraction. In the detailed TD–DFT (time‐dependent density functional theory) studies, the yellow emission appears to be derived from the inter‐ligand charge transfer and metal‐to‐ligand charge transfer (M +L ′)→LCT excited state (LCT is ligand charge transfer).  相似文献   

11.
The self‐assembly of ditopic bis(1H‐imidazol‐1‐yl)benzene ligands ( L H) and the complex (2,2′‐bipyridyl‐κ2N,N′)bis(nitrato‐κO)palladium(II) affords the supramolecular coordination complex tris[μ‐bis(1H‐imidazol‐1‐yl)benzene‐κ2N3:N3′]‐triangulo‐tris[(2,2′‐bipyridyl‐κ2N,N′)palladium(II)] hexakis(hexafluoridophosphate) acetonitrile heptasolvate, [Pd3(C10H8N2)3(C12H10N4)3](PF6)6·7CH3CN, 2 . The structure of 2 was characterized in acetonitrile‐d3 by 1H/13C NMR spectroscopy and a DOSY experiment. The trimeric nature of supramolecular coordination complex 2 in solution was ascertained by cold spray ionization mass spectrometry (CSI–MS) and confirmed in the solid state by X‐ray structure analysis. The asymmetric unit of 2 comprises the trimetallic Pd complex, six PF6? counter‐ions and seven acetonitrile solvent molecules. Moreover, there is one cavity within the unit cell which could contain diethyl ether solvent molecules, as suggested by the crystallization process. The packing is stabilized by weak inter‐ and intramolecular C—H…N and C—H…F interactions. Interestingly, the crystal structure displays two distinct conformations for the L H ligand (i.e. syn and anti), with an all‐syn‐[Pd] coordination mode. This result is in contrast to the solution behaviour, where multiple structures with syn/anti‐ L H and syn/anti‐[Pd] are a priori possible and expected to be in rapid equilibrium.  相似文献   

12.
Two one‐dimensional (1D) coordination polymers (CPs), namely catena‐poly[[[aqua(2,2′‐bipyridine‐κ2N,N′)(nitrato‐κO)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′] nitrate], {[Cu(NO3)(C10H8N2)(C13H14N2)(H2O)]·NO3}n ( 1 ), and catena‐poly[[[aqua(nitrato‐κO)(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′] nitrate], {[Cu(NO3)(C12H8N2)(C13H14N2)(H2O)]·NO3}n ( 2 ), have been synthesized using [Cu(NO3)(NN)(H2O)2]NO3, where NN = 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen), as a linker in a 1:1 molar ratio. The CPs were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray structure determination. The 1,3‐bis(pyridin‐4‐yl)propane (dpp) ligand acts as a bridging ligand, leading to the formation of a 1D polymer. The octahedral coordination sphere around copper consists of two N atoms from bpy for 1 or phen for 2 , two N atoms from dpp, one O atom from water and one O atom from a coordinated nitrate anion. Each structure contains two crystallographically independent chains in the asymmetric unit and the chains are linked via hydrogen bonds into a three‐dimensional network.  相似文献   

13.
catena‐Poly[[[tetra­aqua­nickel(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] thio­sulfate dihydrate], {[Ni(C10H8N2)(H2O)4]S2O3·2H2O}n, (I), and catena‐poly[[[tetra­aqua­nickel(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] sulfate methanol solvate monohydrate], {[Ni(C10H8N2)(H2O)4]SO4·CH4O·H2O}n, (II), are built up of {[Ni(4,4′‐bipy)(H2O)4]2+}n chains (4,4′‐bipy is 4,4′‐bipyridine) inter­woven in an unusual P31 fashion. Voids are filled by the corresponding counter‐anions and solvate mol­ecules, defining a complex three‐dimensional network surrounding them. In both structures, the cationic chains evolve around a set of twofold axes passing through the NiII ions and bis­ecting the aromatic amines through their N (and their opposite C) atoms.  相似文献   

14.
The first structure report of trichlorido[4′‐(p‐tolyl)‐2,2′:6′,2′′‐terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl3(C22H17N3)]·C2H6OS, (I), is presented, along with a higher‐symmetry setting of previously reported bis[4′‐(p‐tolyl)‐2,2′:6′,2′′‐terpyridine]iridium(III) tris(hexafluoridophosphate) acetonitrile disolvate, [Ir(C22H17N3)2](PF6)3·2C2H3N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007). Eur. J. Inorg. Chem. pp. 1911–1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent molecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group. The iridium complex and one PF6 anion lie on twofold axes in this structure, making half of the molecule unique.  相似文献   

15.
The title PtII complexes, viz. (2,2′‐bi­pyridine‐κ2N,N′)[(1R,2R)‐1,2‐di­amino­cyclo­hexane‐κ2N,N′]­platinum(II) bis­(hexa­fluoro­phosphate), [Pt(C6H14N2)(C10H8N2)](PF6)2, and [(1R,2R)‐1,2‐di­amino­cyclo­hexane‐κ2N,N′](1,10‐phenanthroline‐κ2N,N′)platinum(II) bis­(hexa­fluoro­phosphate), [Pt(C6H14N2)(C12H8N2)](PF6)2, containing an aromatic α‐di­imine and a non‐planar di­amino­cyclo­hexane, both form a ladder‐type structure, which is constructed via loose π–π stacking on the α‐di­imine ligands and hydrogen bonding between the cyclic amines and the counter‐anions. In the former compound, there are two independent complex cations, both of which have a twofold axis through the Pt atom.  相似文献   

16.
The compound [2‐(aminomethyl)pyridine‐κ2N,N′][chlorido/trifluoromethanesulfonato(0.91/0.09)][(10,11‐η)‐5H‐dibenzo[a,d]cyclohepten‐5‐amine‐κN](triphenylphosphane‐κP)ruthenium(II) trifluoromethanesulfonate dichloromethane 0.91‐solvate, [Ru(CF3SO3)0.09Cl0.91(C6H8N2)(C15H13N)(C18H15P)]CF3SO3·0.91CH2Cl2, belongs to a series of RuII complexes that had been tested for transfer hydrogenation, hydrogenation of polar bonds and catalytic transfer hydrogenation. The crystal structure determination of this complex revealed disorder in the form of two different anionic ligands sharing the same coordination site, which other spectroscopic methods failed to characterize. The reduced catalytic activity of the title compound was not fully understood until the crystallographic data provided evidence for the mixed ligand species. The crystal structure clearly shows that the majority of the synthesized material has a chloride ligand present. Only a small portion of the material is the expected complex [RuII(OTf)(ampy)(η2‐tropNH2)(PPh3)]OTf, where OTf is triflate or trifluoromethanesulfonate, ampy is 2‐(aminomethyl)pyridine and tropNH2 is 5H‐dibenzo[a,d]cyclohepten‐5‐amine.  相似文献   

17.
Crystal structures are reported for four (2,2′‐bipyridyl)(ferrocenyl)boronium derivatives, namely (2,2′‐bipyridyl)(ethenyl)(ferrocenyl)boronium hexafluoridophosphate, [Fe(C5H5)(C17H15BN2)]PF6, (Ib), (2,2′‐bipyridyl)(tert‐butylamino)(ferrocenyl)boronium bromide, [Fe(C5H5)(C19H22BN3)]Br, (IIa), (2,2′‐bipyridyl)(ferrocenyl)(4‐methoxyphenylamino)boronium hexafluoridophosphate acetonitrile hemisolvate, [Fe(C5H5)(C22H20BN3O)]PF6·0.5CH3CN, (IIIb), and 1,1′‐bis[(2,2′‐bipyridyl)(cyanomethyl)boronium]ferrocene bis(hexafluoridophosphate), [Fe(C17H14BN3)2](PF6)2, (IVb). The asymmetric unit of (IIIb) contains two independent cations with very similar conformations. The B atom has a distorted tetrahedral coordination in all four structures. The cyclopentadienyl rings of (Ib), (IIa) and (IIIb) are approximately eclipsed, while a bisecting conformation is found for (IVb). The N—H groups of (IIa) and (IIIb) are shielded by the ferrocenyl and tert‐butyl or phenyl groups and are therefore not involved in hydrogen bonding. The B—N(amine) bond lengths are shortened by delocalization of π‐electrons. In the cations with an amine substituent at boron, the B—N(bipyridyl) bonds are 0.035 (3) Å longer than in the cations with a methylene C atom bonded to boron. A similar lengthening of the B—N(bipyridyl) bonds is found in a survey of related cations with an oxy group attached to the B atom.  相似文献   

18.
In the two ruthenium(II)–porphyrin–carbene complexes ­(di­benzoyl­carbenyl‐κC)(pyridine‐κN)(5,10,15,20‐tetra‐p‐tolyl­porphyrinato‐κ4N)­ruthenium(II), [Ru(C15H10O2)(C5H5N)(C48H36N4)], (I), and (pyridine‐κN)(5,10,15,20‐tetra‐p‐tolyl­porphyrinato‐κ4N)[bis(3‐tri­fluoro­methyl­phenyl)­carbenyl‐κC]­ruthenium(II), [Ru(C15H8F6)(C5H5N)(C48H36N4)], (II), the pyridine ligand coordinates to the octahedral Ru atom trans with respect to the carbene ligand. The C(carbene)—Ru—N(pyridine) bonds in (I) coincide with a crystallographic twofold axis. The Ru—C bond lengths of 1.877 (8) and 1.868 (3) Å in (I) and (II), respectively, are slightly longer than those of other ruthenium(II)–porphyrin–carbene complexes, owing to the trans influence of the pyridine ligands.  相似文献   

19.
The complexes {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ2P,P′}(η4‐norbornadiene)rhodium(I) tetrafluoridoborate, [Rh(C7H8)(C36H28OP2)]BF4, and {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ2P,P′}[η4‐(Z,Z)‐cycloocta‐1,5‐diene]rhodium(I) tetrafluoridoborate dichloromethane monosolvate, [Rh(C8H12)(C36H28OP2)]BF4·CH2Cl2, are applied as precatalysts in redox‐neutral atomic‐economic propargylic CH activation [Lumbroso et al. (2013). Angew. Chem. Int. Ed. 52 , 1890–1932]. In addition, the catalytically inactive pentacoordinated 18‐electron complex {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ2P,P′}chlorido(η4‐norbornadiene)rhodium(I), [RhCl(C7H8)(C36H28OP2)], was synthesized, which can form in the presence of chloride in the reaction system.  相似文献   

20.
The crystal structure of a prospective olefin catalyst, namely {2‐[1‐acetyl‐5‐(2‐hydroxy­phenyl)‐4‐phenyl‐1,2,4‐di­aza­phospholan‐3‐yl]­phenyl acetate‐κP}chloro­(η4‐cyclo­octa‐1,5‐diene)rhodium(I) di­chloro­methane solvate, [RhCl(C8H12)(C24H23N2O4P)]·CH2Cl2, has been determined at 173 K. The five‐membered heterocycle of the phosphine ligand is in a slightly distorted twist conformation. An intramolecular N1—H1⃛Cl1 hydrogen bond contributes to the adopted conformation and may additionally participate in secondary interactions with substrates during catalysis.  相似文献   

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