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1.
The use of pyridine‐2,4‐dicarboxylic acid (H 2pydc) in the construction of Sr II and Sr II‐M II (M=Co, Ni, Zn and Cu) coordination polymers is reported. Eight complexes, that is, [Sr(pydc)H 2O] n ( 1 ), [MSr(pydc) 2(H 2O) 2] n (M=Co ( 2 ), Ni ( 3 ), Zn ( 4 )), [ZnSr(pydc) 2(H 2O) 7] n?4 nH 2O ( 5 ), [SrCu(pydc) 2] n ( 6 ), [SrCu(pydc) 2(H 2O) 3] n?2 nH 2O ( 7 ), and [Cu 3Sr 2(pydc) 4(Hpydc) 2(H 2O) 2] n ( 8 ), have been synthesized via dexterously choosing the appropriate strontium sources and transition metal salts, and rationally controlling the temperature of the reaction systems. Complexes 1 , 2 ( 3 , 4 ), 6 , and 8 display four types of 3‐D framework structures. Complexes 5 and 7 exhibit a 2‐D network and a 1‐D chain structure, respectively. The 2‐D complex 7 can be reversibly transformed into 3‐D compound 6 through temperature‐induced solvent‐mediated structural transformation. The luminescent property studies indicated that complex 1 shows a strong purple luminescent emission and 4 exhibits a strong violet luminescence emission. The magnetic properties of 2 , 3 , and 8 were also studied. Antiferromagnetic M II???M II interactions were determined for these complexes. 相似文献
2.
The interactions of ciprofloxacin (HCipro) with transition metals have been investigated. Two types of complexes, [M(Cipro)(OAc)(H 2O) 2] · 3H 2O (M = Mn II, Co II, Cu II or Cd II) and [M(Cipro)(OAc)] · 6H 2O (M = Ni II or Zn II), were obtained and characterized by physicochemical and spectroscopic methods. The i.r. spectra of the complexes suggest that the ciprofloxacin behaves as a monoanionic bidentate ligand. In vitro antibacterial activities of the HCipro and the complexes were tested. 相似文献
3.
Four Cu II and Co II complexes–[Cu(L 1)Cl 2(H 2O)]3/2H 2O · 1/2EtOH, [Cu(L 1) 2Cl 2]6H 2O, [Co(L 1)Cl 2]3H 2O · EtOH, and [Co 2(L 1)(H 2O)Cl 4]1.5H 2O · EtOH (L 1 = 2,4,6-tri(2-pyridyl)-1,3,5-triazine; TPT)–were synthesized by conventional chemical method and used to synthesize another four metal complexes–[Cu(L 1)I 2(H 2O)]6H 2O, [Cu(L 1) 2I 2]6H 2O, [Co(L 1)I(H 2O) 2]I · 2H 2O, and [Co 2(L 1)I 4(H 2O) 3]–using tribochemical reaction, by grinding it with KI. Substitution of chloride by iodide occurred, but no reduction for Cu II or oxidation of Co II. Oxidation of Co II to Co III complexes was only observed on the dissolution of Co II complexes in d 6-DMSO in air while warming. The isolated solid complexes (Cu II and Co II) have been characterized by elemental analyses, conductivities, spectral (IR, UV-Vis, 1H-NMR), thermal measurements (TGA), and magnetic measurements. The values of molar conductivities suggest non-electrolytes in DMF. The metal complexes are paramagnetic. IR spectra indicate that TPT is tridentate coordinating via the two pyridyl nitrogens and one triazine nitrogen forming two five-membered rings around the metal in M : L complexes and bidentate via one triazine nitrogen and one pyridyl nitrogen in ML 2 complexes. In binuclear complexes, L is tridentate toward one Co II and bidentate toward the second Co II in [Co 2(L 1)Cl 4]2.5H 2O · EtOH and [Co 2(L 1)I 4(H 2O) 3]. Electronic spectra and magnetic measurements suggest a distorted-octahedral around Cu II and high-spin octahedral and square -pyramidal geometry around Co II. 相似文献
4.
Summary Complexes of the type M(AcLeu) 2 · B 2 (M = Co II, Ni II or Zn II; B = H 2O, py, 3-pic, 4-pic; AcLeu = N-acetyl-DL-leucinate ion) and M(AcLeu) 2 B (M = Co II or Zn II and B = o-phen) were prepared and investigated by means of magnetic and spectroscopic measurements. The i.r. spectra of all the complexes are consistent with bidentate coordination of the amino acid to the metal ion. The room temperature solid state electronic spectra indicate that the symmetry of this species is closer to D
4h
and that MO 6 and MO 4N 2 chromophores are present in the M(AcLeu) 2 · 2 H 2O and M(AcLeu) 2B n · x H 2O (B = py, 3-pic, 4-pic, n=2 and x=0 for M = Ni II; B = o-phen, n=1 and x=0 for M = Co II; B = py, 3-pic, 4-pic, n=1 and x=1 for M = Co II) complexes, respectively. By comparing the Dq values of the amino acid and those of other N-substituted amino acids previously studied, a spectrochemical series of the the cobalt(II) and nickel(II) complexes is proposed. The 1 H n.m.r. spectra of the zinc(II) complexes confirm the proposed stereochemistry. 相似文献
5.
Two heterospin complexes [Cu(NIT3Py)(cda)H 2O] · H 2O ( 1 ) and [Cu(NIT2Py)(cda)H 2O] · H 2O · CH 3OH ( 2 ) with Cu II ions and pyridyl‐substituted nitronyl nitroxide radicals (NIT xPy = 2‐( x′‐pyridyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide, x = 3, 2; H 2cda = 4‐hydroxy‐pyridine‐2,6‐dicarboxylic acid) were synthesized and characterized structurally and magnetically. The single crystal structures show that the two complexes are both two‐spin complexes, in which the different radicals make the two complexes have different hydrogen bonding interactions to form 2D and 1D supramolecular network for complexes 1 and 2 , respectively. The magnetic measurements indicate that complexes 1 and 2 both exhibit antiferromagnetic interactions between Cu II and radicals. 相似文献
6.
Three coordination polymers, namely [Co(BDC)( L )] · H 2O ( 1 ), [Co(NPH)( L )] · H 2O ( 2 ), and [Ni(NPH)( L )(H 2O) 3] · H 2O ( 3 ) [H 2BDC = 1, 3‐benzenedicarboxylic acid, H 2NPH = 3‐nitrophthalic acid, L = N, N′‐bis(3‐pyridyl)‐terephthalamide] were hydrothermally synthesized by self‐assembly of cobalt/nickel chloride with a semi‐rigid bis‐pyridyl‐bis‐amide ligand and two aromatic dicarboxylic acids. Single crystal X‐ray diffraction analyses revealed that complexes 1 and 2 are two‐dimensional (2D) coordination polymers containing a one‐dimensional (1D) ribbon‐like Co‐dicarboxylate chain and a 1D zigzag Co‐ L chain. Although the coordination numbers of Co II ions and the coordination modes of two dicarboxylates are different in complexes 1 and 2 , they have a similar 3, 5‐connected {4 2.6 7.8}{4 2.6} topology. In complex 3 , the adjacent Ni II ions are linked by L ligands to form a 1D polymeric chain, whereas the 1D chains does not extend into a higher‐dimensional structure due to the ligand NPH with monodentate coordination mode. The adjacent layers of complexes 1 and 2 and the adjacent chains of 3 are further linked by hydrogen bonding interactions to form 3D supramolecular networks. Moreover, the thermal stabilities, fluorescent properties, and photocatalytic activities of complexes 1 – 3 were studied. 相似文献
7.
Summary The preparation and characterization of Cu II, Co II, Ni II and Hg II complexes containing 1,4-diphenylthiosemicarbazide (DPhTSC) of the type [Cu(DPhTSC-H)X.H 2O]nH 2O (X= Cl, Br or Ac; n=0 or 1) · [M(DPhTSC-H) 2yH 2O] (M=Co II or Ni II; y=0 or 1) and [Hg(DPhTSC)Cl 2]2 H 2O and [Cu(D-PhTSC) 2SO 4]H 2O are reported. The stereochemistry of the complexes have been studied with the help of magnetic and electronic measurements. The anomalous magnetic moments observed in all cases have been explained. The i.r. spectral studies have been used to determine the bonding sites in the complexes. 相似文献
8.
4,6-Diacetylresorcinol serves as a starting point for the generation of multidentate S/N/O or O/N/O symmetrical chelating agents by condensation with thiosemicarbazide or semicarbazide to yield the corresponding bis(thiosemicarbazone) H 4L 1 or bis(semicarbazone) H 4L 2, respectively. Reaction of H 4L 1 and H 4L 2 with M(NO 3) 2·6H 2O (M?=?Co or Ni) afforded dimeric complexes for H 4L 1 and binuclear complexes for H 4L 2, revealing the tendency of S to form bridges. The dimeric cobalt complexes of H 4L 1 are very interesting in that they contain Co II/Co III, side/side, low-spin octahedral coordinated Co III-ions and high-spin square-planar coordinated Co II-ions. These complexes have the general formula [(H 2L 1) 2Co 2(H 2O) (NO 3)]· nEtOH. Arguments supporting these anomalous Co II/Co III structures are based on a pronounced decrease in their magnetic moments, elemental and thermal analyses, visible and IR spectra, as well as their unreactivity towards organic bases such as 1,10-phenanthroline (phen), 2,2′-bipyridine (Bpy), N, N, N′, N′-tetramethylethylenediamine (Tmen) and 8-hydroxyquinoline (oxine, Ox). The dimeric octahedral Ni II complex [(H 2L 1) 2Ni 2(H 2O) 4]·3H 2O showed higher reactivity towards phen and Bpy and formed adducts; [(HL 1)Ni 2(B)(H 2O) 5] NO 3 (B?=?phen or Bpy). In the presence of oxine, the dimeric brown paramagnetic octahedral complex [(H 2L 1) 2Ni 2(H 2O) 4]·3H 2O was transformed to the dimeric brick-red diamagnetic square-planar complex [(H 3L 1) 2Ni 2](NO 3) 2. The latter showed dramatic behavior in its 1H NMR spectrum in DMSO- d 6, which was explained on the basis of H +-transfer. By contrast, the binuclear Ni II–H 4L 2 complex ( 11) showed higher reactivity towards phen, Bpy and oxine. These reactions afforded mixed dimeric complexes having the molar ratio 2?:?2?:?1 (Ni II?:?H 4L 2?:?base). The binuclear Co II–H 4L 2 complex afforded an adduct with phen and trinuclear complexes with Bpy and oxine. All complexes were found to be unreactive towards Tmen. Structural characterization was achieved by elemental and thermal analyses, spectral data (electronic, IR, mass and 1H NMR spectra) and conductivity and magnetic susceptibility measurements. 相似文献
9.
Three Zn II and Cd II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L 1)(2,2′‐bpy) 2(H 2O)] · 2H 2O ( 1 ), [Zn(L 1)(bpp)(H 2O)] ( 2 ), and [Cd(L 1)(H 2O)] · H 2O ( 3 ) [H 2L 1 = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8 2). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated. 相似文献
10.
Summary 2-Aminoacetophenone-2-thenoylhydrazone, Haath, C 4H 3SC(O)NHN=C(Me)C 6H 4NH 2- o, forms complexes with metal(II) salts of empirical compositions [VO(Haath) 2SO 4], [M(Haath) 2Cl 2] [M=Co II, Ni II, Cu II or Zn II] and [M(aath) 2] [M=V IVO, Co II, Ni II, Cu II or Zn II] which have been characterized by elemental analyses, molar conductance, magnetic susceptibility, electronic, e.s.r., i.r. and n.m.r. ( 1H and 13C) spectral studies. X-ray and electron diffraction patterns have been obtained in order to elucidate the structure of the Cu II complexes. Photoacoustic spectra of powder Ni II complexes have been recorded and interpreted in the light of u.v./vis. spectra. 相似文献
11.
Three coordination polymers, namely {[Cu(5‐nipa)(L 22)](H 2O) 2} n ( 1 ), [Zn(5‐nipa)(L 22)(H 2O)] n ( 2 ), and {[Cd 2(5‐nipa) 2(L 22)(H 2O) 3](H 2O) 3.6} n ( 3 ), were prepared under similar synthetic method based on 1,2‐(2‐pyridyl)‐1,2,4‐triazole (L 22) and ancillary ligand 5‐nitro‐isophthalic acid (5‐H 2nipa) with Cu II, Zn II, and Cd II perchlorate, respectively. All the complexes were characterized by IR spectroscopy, elemental analysis, and powder X‐ray diffraction (PXRD) patterns. Single‐crystal X‐ray diffraction indicates that complexes 1 and 2 show similar 1D chain structures, whereas complex 3 exhibits the 2D coordination network with hcb topology. The central metal atoms show distinct coordination arrangements ranging from distorted square‐pyramid for Cu II in 1 , octahedron for Zn II in 2 , to pentagonal‐bipyramid for Cd II in 3 . The L 22 ligand adopts the same (η 3,μ 2) coordination fashion in complexes 1 – 3 , while the carboxyl groups of co‐ligand 5‐nipa 2– adopt monodentate fashion in 1 and 2 and bidentate chelating mode in 3 . These results indicate that the choice of metal ions exerts a significant influence on governing the target complexes. Furthermore, thermal stabilities of complexes 1 – 3 and photoluminescent properties of 2 and 3 were also studied in the solid state. 相似文献
12.
Metallo-guanines of the type [M(G) 2·2H 2O] [M = Ni II, Fe II, Cu II and UO 2
II; G = anionic guanine], [M(G) 2(GH)· H 2O] (M = Co II and Mn II; GH = neutral guanine), [Pd(G) 2]·2H 2O and [Zn(G)Cl] 2 have been isolated and characterised. Anionic guanine functions as a bidentate ligand and links through N(3) and N(9). E.p.r. data indicate that the Cu II complex has a highly distorted octahedral structure. The magnetic susceptibility data suggest that the Co II and Ni II complexes possess pseudooctahedral geometry. Neutral guanines are probably unidentate and coordinate either through N(3) or N(9). The isolated guanosine complexes are of the types: [M(Gs) 2·H 2O] [M = Ni II and Cu II, Gs = anionic guanosine] [Pd(Gs) 2]·2H 2O and [UO 2(Gs) 2]. I.r. data indicate that guanosine also functions as a bidentate ligand, but coordinates through N(1) and C 2 — NH 2. The electronic absorption spectra of the complexes indicate that guanine is a stronger ligand than guanosine. 相似文献
13.
Summary N-Cyano-N-methyl-N(2-[(5-methyl-1H-imidazol-4-yl)-methylthio] ethyl) guanidine cimetidine (CM), complexes with Co II, Ni II and Cu II are described. The compounds are of stoichiometry [M(CM) 2]SO 4 · nH 2O [M = Co II, Ni II or Cu II; n = 3,3 or 4, respectively], [M(CM) 2](ClO 4) 2 [M = Co II or Ni II], [M(CM) 2]Cl 2 · nH 2O [M=Co II, Ni II or Cu II; n = 1, 2, or 2, respectively] and [Cu(CM)SO 4] · 2H 2O. The electronic spectra of the compounds in solid state, magnetic susceptibilities and i.r. and e.p.r. spectra were studied. Octahedral environments are proposed for the complexes: [M(CM) 2]SO 4·nH 2O, [M(CM) 2](ClO 4) 2, [Ni(CM) 2]Cl 2 · 2H 2O, [Cu(CM) 2]Cl 2 · 2H 2O and [Cu(CM)SO 4] · 2H 2O and a tetrahedral structure for [Co(CM) 2]Cl 2 · H 2O. 相似文献
14.
Transition metal complexes of Co II, Ni II and Cu II with 4-(4-azidosulfophenylazo)-5-phenyl-3,4-dihydro-2H-pyrazol-3-oneHL 1, 4-(4-azidosulfophenylazo)-5-methyl-2-phenyl-3,4-dihydro-2H-pyrazol-3-one HL 2 and 4-(3-azidosulfo-6-methoxyphenylazo)-5-methyl-2-phenyl-3,4-dihydro-2H-pyrazol-3-one HL 3 were prepared and characterized by elemental analyses, molar conductances and magnetic susceptibilities and by i.r., electronic and e.s.r. spectral measurements as well as thermal (d.t.a and t.g.a.) analysis. The i.r. spectra indicate that HL acts as a bidentate ligand coordinating via the azo and enolic-oxygen linkages. The electronic spectral data and magnetic moments suggest a tetragonally distorted octahedral geometry for the complexes having the formula ML 2·2H 2O, (M = Co II, Ni II and Cu II), square pyramidal geometry for CuL
2
3
H 2O and tetrahedral geometry for CoL
2
3
. The X-band e.s.r. spectra of the copper(II) complexes reveal anaxial symmetry for both CuL
2
2
2H 2O and CuL
2
3
H 2O while CuL
2
1
O is isotropic in the solid state at room temperature. The d.t.a. curves show two exothermic peaks for all three complexes CoL
2
3
,NiL
2
3
2H 2O and CuL
2
3
H 2O and one endothermic peak for the latter two aqua complexes. 相似文献
15.
Reactions of Mn(II) and Cd(II) salts with 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazole (HL) under hydrothermal conditions result in complexes [Mn(L)2(H2O)4] · 2H2O (I) and [Cd(L)2(H2O)2] (II), which have been characterized by single crystal and powder X-ray diffractions (CIF files CCDC nos. 943861 (I), 943862 (II)), IR spectroscopy, element and thermogravimetric analyses. Two complexes exhibit structural diversity dependent on different metal salts. Complex I shows discrete mononuclear structure, which can be further linked to build a 3D supramolecular framework through hydrogen bonding interactions. Complex II displays 1D zigzag-chain structure, and an extended 3D framework can be formed by hydrogen bonding. Interestingly, tetranuclear water clusters were generated in I, which can be linked by Mn2+ ions to show 1D metal-bridged water cluster-chain structure. The present work provides an example that metal centers impact on coordination modes of ligand and consequent structural variation of resulted complexes. Moreover, fluorescence property of II was investigated. 相似文献
16.
Summary Reactions of glyoxal bis(morpholine N-thiohydrazone), H 2gbmth, with NiCl 2·6H 2O, Ni(OAc) 2·4H 2O, Ni(acac) 2· H 2O, CuCl 2·2H 2O, Cu(OAc) 2·H 2O, Cu(acac) 2, CoCl 2· 6H 2O, Co(OAc) 2·4H 2O and Co(acac) 2·2H 2O yield complexes of the type [M(gbmth)], [M=Ni II, Cu II or Co II]. Diacetyl reacts with morpholine N-thiohydrazide in the presence of nickel salts to yield [Ni II(dbmth)], [Ni II(dmth)(OAc)]H 2O and [Ni II(Hdmth)(NH 3)Cl 2] involving N 2S 2 and NSO donor ligands. Copper and cobalt complexes of N 2S 2 and NSO donor ligands with compositions [Cu II(dbmth)], [Co II(dbmth)]·4H 2O and [Co II(H 2dbmth)]Cl 2, have been isolated. The compounds have been characterised by elemental analyses, magnetic moments, molar conductance values and spectroscopic (electronic and infrared) data. 相似文献
17.
Reaction of a imidazole phenol ligand 4‐(imidazlo‐1‐yl)phenol (L) with 3d metal salts afforded four complexes, namely, [Ni(L) 6] · (NO 3) 2 ( 1 ), [Cu(L) 4(H 2O)] · (NO 3) 2 · (H 2O) 5 ( 2 ), [Zn(L) 4(H 2O)] · (NO 3) 2 · (H 2O) ( 3 ), and [Ag 2(L) 4] · SO 4 ( 4 ). All complexes are composed of monomeric units with diverse coordination arrangements and corresponding anions. All the hydroxyl groups of monomeric cations are used as hydrogen‐bond donors to form O–H ··· O hydrogen bonds. However, the coordination habit of different metal ions produces various supramolecular structures. The Ni II atom shows octahedral arrangement in 1 , featuring a 3D twofold inclined interpenetrated network through O–H ··· O hydrogen bond and π–π stacking interaction. The Cu II atom of 2 displays square pyramidal environment. The O–H ··· O hydrogen bond from the [Cu(L) 4(H 2O)] 2+ cation and lattice water molecule as well as π–π stacking produce one‐dimensional open channels. NO 3– ions and lattice water molecules are located in the channels. 3 is a 3D supramolecular network, in which Zn II has a trigonal bipyramid arrangement. Two different rings intertwined with each other are observed. The Ag I in 4 has linear and triangular coordination arrangements. The mononuclear units are assembled into a 1D chain by hydrogen bonding interaction from coordination units and SO 42– anions. 相似文献
18.
Summary 3-Isonicotinamido-rhodanine (HINRd) reacts with metal ions to yield complexes of the types M(INRd)OH·nH 2O (where M=Co II, Ni II, Zn II or Cd II and n=1 or 2), Cu(HINRd)X·2H 2O (where X=Cl or Br), Pd(HINRd)Cl 2 and Cd(HINRd)X 2·H 2O (where X=Cl or Br), depending on the metal salt used and the reaction conditions. The metal complexes have been characterized by elemental analysis, molar conductivities, molecular weights, magnetic susceptibility, visible, and i.r. studies. The i.r. spectra show that HINRd binds in a bidentate or monodentate manner. The spectral and magnetic studies suggest a tetrahedral arrangement for Co II, octahedral for Ni II and square-planar for Pd II. HINRd behaves as a reducing agent towards Cu II chloride or bromide forming diamagnetic Cu I complexes. 相似文献
19.
Summary Bivalent metal complexes of p-chloro-, p-methyl- and p-methoxybenzoylhydrazone oximes (H 2BMCB, H 2BMMB or H 2BMTB=H 2L), [M(H 2L)Cl 2]. nH 2O (M=Zn II, Cd II or Hg II, n=0 or 1; [M(H 2L)Cl 2] (M=Zn II or Cd II); [M(HL) 2(H 2O) n]. YH 2O (M=Co II, Cu II, Zn II or U VIO 2, n=0–2); [Ni(H 2BMCB)(H 2O) 3]Cl 2, [Ni(BMMB)(H 2O)] 2 and [Ni(BMTB)(H 2O)] 2, were synthesized by conventional physical and chemical measurements. I.r. spectra show that the ligands are bidentate or tridentate. Spectral, magnetic and molecular weight measurements suggest that cobalt(II) and nickel(II) have monomeric octahedral geometry when derived from H 2BMCB, a dimeric square planar geometry for nickel(II) and monomeric square planar geometry for cobalt(II) for those isolated from H 2BMMB or H 2BMTB. Also, a monomeric distorted octahedral structure is proposed for copper(II) complexes derived from the ligands under investigation. 相似文献
20.
Three 1H‐benzimidazole‐5‐carboxylate (Hbic –)‐based coordination polymers, {[Ni(H 2O)(Hbic) 2] · 2H 2O} n ( 1 ), {[Ni(H 2O) 2(Hbic) 2] · 3H 2O} n ( 2 ), and {[Co 2(H 2O) 4(Hbic) 4] · 4DMF · 3H 2O} n ( 3 ) were obtained by reactions of the ligand H 2bic and Ni II or Co II salts in the presence of different structure directing molecules. They were structurally characterized by single‐crystal X‐ray diffraction, IR spectra, elemental analysis, thermal stability, luminescent, and magnetic measurements. Structural analysis suggests that the three polymers exhibit a 2D (4, 4) layer for 1 and 1D linear double chains for both 2 and 3 due to the variable binding modes and the specific spatial orientation of the Hbic – ligand towards the different paramagnetic metal ions, which were further aggregated into different 3D supramolecular architectures by popular hydrogen‐bonding interactions. Weak and comparable antiferromagnetic couplings mediating by Hbic – bridge are observed between the neighboring spin carriers for 2 and 3 , respectively. Additionally, complexes 1 – 3 also display different luminescence emissions at room temperature due to the ligand‐to‐metal charge transfer. 相似文献
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