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Issue 5, 2013
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Bisactinyl halogenated complexes: relativistic density functional theory calculation and experimental synthesis

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Abstract

Relativistic density functional theory was used to explore a series of bisactinyl complexes, [(phen)(AnVIO2)(μ2-F)(F)]2 (An = U (1), Np (2) and Pu (3); phen = phenanthroline; μ2 = doubly bridged), [(phen)(UVO2)(μ2-F)(F)]22− (4), [(phen)(UVIO2)(μ2-X)(X)]2 (X = Cl (5), Br (6) and I (7)), [(L)(UVIO2)(μ2-F)(F)]2 (L = bpy (8), 2NH3 (9) and 2F (10); bpy = 2,2′-bipyridine) and [NH4]4[(F)2(UVIO2)(μ2-F)(F)]2 (11). The effects of varying actinyl ions (UO22+, NpO22+ and PuO22+), oxidation states of uranium (VI and V) and equatorial ligands (phen → bpy → 2NH3 → 2F and F → Cl → Br → I) on the structures and electronic properties of complexes were examined. The calculated distances and bond orders of An[double bond, length as m-dash]O indicate the partial triple bonding character, and agree with the trends in the An[double bond, length as m-dash]O stretching vibrational frequencies. The free energies of formation reactions of 1–11 calculated in the aqueous solution demonstrate that 1, 8 and 11 are thermodynamically stable. In this work, we have successfully synthesized 1 and [Me2NH2]4[(F)2(UVIO2)(μ2-F)(F)]2 (12), which is represented by theoretical model complex 11. Their characterizations of the single crystal X-ray diffraction and infrared are consistent with the calculated results; the measured fine-structured fluorescent emissions were assigned as transitions from the U[double bond, length as m-dash]O bonding to the U (f) orbital by analyzing the electronic structure and absorption spectra.

Graphical abstract: Bisactinyl halogenated complexes: relativistic density functional theory calculation and experimental synthesis

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Publication details

The article was received on 06 Jul 2012, accepted on 13 Nov 2012 and first published on 14 Nov 2012


Article type: Paper
DOI: 10.1039/C2RA21370B
Citation: RSC Adv., 2013,3, 1572-1582
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    Bisactinyl halogenated complexes: relativistic density functional theory calculation and experimental synthesis

    Q. Pan, Y. Wang, R. Wang, H. Wu, W. Yang, Z. Sun and H. Zhang, RSC Adv., 2013, 3, 1572
    DOI: 10.1039/C2RA21370B

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