Comparison of ionization potentials of unexcited atoms and ions calculated by different methods

A model differential equation relating the vertical ionization potentials of unexcited atoms and ions of elements is obtained; its solution establishes the relation between these quantities and the spectroscopic index of the electron expressed by an exponential. On the basis of this relation, the ionization potentials calculated in various works are compared. Using the model equation proposed here, it is possible to calculate unknown and refine known ionization potential values.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 14–17, November, 1984.     

pH-controlled photoinduced electron transfer in the [(Mo6Cl8)L6]-calix[4]resorcine-dimethylviologen system

A pH-controlled photoinduced electron transfer in the supramolecular system [(Mo(6)Cl(8))L(6)]-calix[4]resorcine-dimethylviologen is reported.     

Synthesis and characterization of [PW11O39Ir(H2O)]4-: successful incorporation of Ir into polyoxometalate framework and study of the substitutional lability at the Ir(III) site

The first Keggin-type heteropolyanion, [PW(11)O(39)Ir(H(2)O)](4-) (1), was synthesized by hydrothermal reaction from two different polytungstate precursors and [IrF(6)](2-). It was isolated as (Bu(4)N)(4)[PW(11)O(39)Ir(H(2)O)] (1a), which was completely characterized by multinuclear (31)P and (183)W NMR, ESI-mass spectrometry and cyclic voltammetry. A rapid screening methodology to ascertain the intrinsic substitutional lability at the Ir site is also presented, based on ESI-MS.     

Synthesis and Structure of [Co(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>]<Subscript>2</Subscript>[W<Subscript>4</Subscript>Se<Subscript>4</Subscript>(CN)<Subscript>12</Subscript>]·8.5H<Subscript>2</Subscript>O

The compound [Co(NH₃)₆]₂[W₄Se₄(CN)₁₂]·8.5H₂O was obtained by evaporating an aqueous ammonia solution of K₆[W₄Se₄(CN)₁₂]·6H₂O and CoCl₂·6H₂O complexes. The starting Co(II) of CoCl₂·6H₂O transforms into [Co(NH₃)₆]³⁺ when exposed to air in a water-ammonia medium. Crystal data: triclinic crystal system, a = 10.7750(8) Å, b = 12.2843(9) Å, c = 19.6539(14) Å; α = 90.213(2)°, β = 99.910(2)°, γ = 114.737(1)°, V = 2319.1(3) ų, space group , Z = 2, D _x = 2.633 g/cm³.Original Russian Text Copyright © 2004 by I. V. Kalinina, Z. A. Starikova, F. M. Dolgushin, D. G. Samsonenko, and V. P. Fedin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 905–908, September–October, 2004.     

Synthesis and structure of [Ni(dien)2]3[W4S4(CN)2]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O

[Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O and [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O were obtained by evaporating water-ammonia solutions containing K₆[W₄S₄(CN)₁₂]·2H₂O·2CH₃OH, diethylene triamine, and NiCl₂·6H₂O or CuCl₂·6H₂O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O are: triclinic system, , a = 14.671(2) Å, b = 16.448(3) Å, c = 19.814(3) Å, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) ų, Z = 2; for the complex [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O: monoclinic system, C2/c, a = 37.4290(1) Å, b = 17.7370(1) Å, c = 25.7370(2) Å, β = 105.3840(2)°, V = 16474.02(16) ų, Z = 12. Original Russian Text Copyright ? 2005 by I. V. Kalinina, D. G. Samsonenko, Z. A. Starikova, A. A. Korlyukov, J. Lipkowski, V. P. Fedin, and M. Yu. Antipin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 139–148, January–February, 2005.     

Synthesis and crystal structures of supramolecular compounds of polynuclear aluminum(III) aqua hydroxo complexes with cucurbit[6]uril

Supramolecular compounds of the di-, trideca-, and triacontanuclear aluminum aqua hydroxo complexes, viz., [Al₂(OH)₂(H₂O)₈]⁴⁺, [Al₁₂(AlO₄)(OH)₂₄(H₂O)₁₂]⁷⁺, and [Al₃₀O₈(OH)₅₆(H₂O)₂₆]¹⁸⁺, respectively, with the organic macrocyclic cavitand cucurbit[6]uril (C₃₆H₃₆N₂₄O₁₂) were prepared by evaporation of aqueous solutions of aluminum nitrate and cucurbit[6]uril after the addition of pyridine, ammonia, KOH, or NaOH at pH 3.1–3.8. X-ray diffraction study demonstrated that the aqua hydroxo complexes are linked to the macrocycle through hydrogen bonds between the hydroxo and aqua ligands of the polycations and the portal oxygen atoms of cucurbit[6]uril. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 261—268, February, 2006.     

The 31P NMR spectra of ArCr(CO)2P(C6H5)3 compounds in neutral and acidic media

The ³¹P NMR spectra of C₆H₅XCr(CO)₂P(C₆H₅)₃ (X = H, CH₃, OCH₃, N(CH₃)₂, COOCH₃) (I), p-C₆H₄X₂Cr(CO)₂P(C₆H₅)₃ (X = COOCH₃)(II) and C₆H₃X₃Cr(CO)₂P(C₆H₅)₃ (X = CH₃) (III) complexes in neutral and acidic media were investigated. The protonation of complexes I and III in trifluoroacetic acid results in the greater upfield shielding of ³¹P{¹H} signal. In this case the complexes I (X = H, CH₃, OCH₃) are completely protonated at the metal, complex I (X = COOCH₃)is partially protonated, while no protonation occurs in the case of complex II.Temperature-dependence of the ³¹P{¹H} NMR spectra was investigated for complexes I (X = H, OCH₃) in a 1/10 mixture of trifluoroacetic acid and toluene and for complexes I (X = COOCH₃) and II in trifluoroacetic acid. The degree of protonation was found to increase with decreasing temperature.