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1981 (1)
1Author    H. Schulz, Yv PreetzRequires cookie*
 Title    Darstellung und spektroskopische Charakterisierung von Tetrachloro-und Tetrabromo-Oxalatoiridaten(IV) Preparation and Spectroscopical Characterization of Tetrachloro-and Tetrabromoiridates(IV)  
 Abstract    On treatment of [IrXß] 2-with oxalate in aqueous solution at first [IrX40x] 3-(X = Cl, Br) is formed, which after extraction with pentylammonium ions into CH2CI0 can be oxidised by X2 to give the corresponding pure Ir(IV) complexes [UXLjox] 2-. The IR and Raman spectra are assigned according to point group C2v-The UV/VIS absorption spectra show strong CT bands of transitions from "(.t + <7)tiu"-and "jrt2U"-ligand niveaus to t2g 5 (Ir IV). These are split into three components by spin-orbit coupling and corresponding to the different groups of ligands: X| r , Xg, ox. The spectrum of (TBA)2[IrBr40x] recorded at 10 K is highly resolved, showing a splitting of the Br£ r ->Ir(IV) and Bg -n>-Ir(IV) transi-tions by 1000-1400 cm -1 . In the NIR-region two d-d-transitions are observed super-imposed with a fine structure by coupling with vibration modes. 
  Reference    Z. Naturforsch. 37b, 1553—1557 (1982); eingegangen am 13. August 1982 
  Published    1982 
  Keywords    Totrahalogenooxalatoiridates(IV), UV-VIS-NIR Spectra, IR Spectra, Raman Spectra 
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 TEI-XML for    default:Reihe_B/37/ZNB-1982-37b-1553.pdf 
 Identifier    ZNB-1982-37b-1553 
 Volume    37 
2Author    G. O. Stendorp3, O. Tterb, H. HomRequires cookie*
 Title    Syntheses and Properties of Cerium Diphthalocyanines in High Oxidation States; Crystal Structure of [C e(Pc)2](BF4) 0.33  
 Abstract    Ring oxidized green Cerium(IV)diphthalocyanines, [Ce(Pc)2]X (X = (poly)halide, N 0 3_) are prepared by chemical oxidation of ("Bu4N)[Ce(Pc2~)2] with the corresponding halogen in solution or of solid [Ce(Pc2_)2] with aqueous HNO> Electrochemical oxidation of ("Bu4N)[Ce(Pc2_)2] in solution in the presence of ("Bu4N)BF4 yields [Ce(Pc)2](BF4)0.;p, which crystallizes in the tetragonal space group P4/nnc (a, b = 19.643(3) A, c = 6.525(3) A, Z = 2). The CeIV ion is eightfold coordinated by the isoindole N atoms (Niso) of the two staggered (ca. 41°), slightly distorted Pc ligands. The "[Ce(Pc)2]<)33+" subunits are arranged in infinite columns along [001] with the Ce atoms statistically disordered over two positions and C e -N iso bond lengths of 2.45(1) and 2.69(1) A, respectively The UV-VIS spectrum is dominated by the transitions of the Pc2-ligand at ca. 15,000 (B band), 30,000 and 36,000 cm -1 (Q, N region). A low energy ("metallic") band at ca. 2800 cm -1 typical for partially oxidized systems is present. The UV-VIS-NIR spectrum of [Ce(Pc)2]N 0 3 indicates a cofacial Pc2" -P c -complex. In addition to the jt-jz' transitions of the Pc2-moiety at ca. 14,000, 30,000 and 36,000 cm-1, the Ch transition of the Pc-ring is observed at ca. 19,200 cm -1 and the typical N IR band at 6380 cm -1. Oxidation of a thin film of (PNP)[Ce(Pc2_)2] with dry Br2/ N2 gas yields purple [Ce(Pc_)2]B rv, whose UV-VIS-NIR spectrum shows the diagnostic fea­ tures of dimeric Pc~ radicals with intense bands at ca. 14,000 and 18,000 cm -1 assigned as B and Qi bands, respectively. A t ca. 9000 cm 1 the typical Q D absorption is observed. The vibrational spectra are dom inated by the transitions of the Pc-ligand at 1305/1445 cm -1 (IR) and 560/1120/1172/1591 cm-1 (resonance Raman). Excitation with 1064 nm strongly enhances the sym. C e -N stretch at 163 c m '1. 
  Reference    Z. Naturforsch. 51b, 567—573 (1996); received September 14 1995 
  Published    1996 
  Keywords    Diphthalocyanines, Cerium Compounds, Crystal Structure, UV-VIS-NIR Spectra, Vibrational Spectra 
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 TEI-XML for    default:Reihe_B/51/ZNB-1996-51b-0567.pdf 
 Identifier    ZNB-1996-51b-0567 
 Volume    51 
3Author    W. Preetz, H. SchulzRequires cookie*
 Title    Darstellung und spektroskopische Charakterisierung von Tetrakis (chlor o -iodo ) oxalato -osmaten (IV )  
 Abstract    On treatment of [OsLjox] 2-with Cl~ the mixed complexes [OsClnI4_nox] 2 -, n = 1, 2, 3, are formed. The isolation and complete separation of the differently coloured geometric isomers is achieved by ion exchange chromatography on diethylaminoethyl cellulose. The IR and Ra spectra are assigned according to point groups Czv, Cs, Ci. The mutual influence of ligands, especially by the high trans effect of I, is indicated by shifts of the distinct vibrational and electronic bands. The observed splittings of I -> Os transitions are attributed to the different groupings I-Os-I, I-Os-Cl, and I-Os-O, important for the distinction of stereoisomers. The CT-bands as well as the d-d-transitions show batho-chromic shifts with increasing number of I-ligands. Up to five spin-orbit components in the NIR region are well resolved. The assignment is improved by the electronic Ra spectra. The fine structure of some d-d-bands originates from coupling with symmetric vibrational modes. 
  Reference    (Z. Naturforsch. 36b, 62—69 [1981]; eingegangen am 10. Oktober 1980) 
  Published    1981 
  Keywords    Tetrakis(chloro-iodo)oxalato-osmates(IV), UV-VIS-NIR Spectra, IR Spectra, Raman Spectra 
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 TEI-XML for    default:Reihe_B/36/ZNB-1981-36b-0062.pdf 
 Identifier    ZNB-1981-36b-0062 
 Volume    36