Crystal structure diversity in the bis[hydrotris-(3,5-dimethylpyrazolyl)borate]iodouranium(III) complex: from neutral to cationic forms

被引：28

作者：

Antunes, Maria Augusta ^{[1
]}

Santos, Isabel C. ^{[1
,2
]}

Bolvin, Helene ^{[3
]}

Pereira, Laura C. J. ^{[1
]}

Mazzanti, Marinella ^{[4
]}

Marcalo, Joaquim ^{[1
]}

Almeida, Manuel ^{[1
]}

机构：

[1] Univ Tecn Lisboa CFMCUL, Inst Super Tecn, IST ITN, Unidade Ciencias Quim & Radiofarmaceut, P-2686953 Sacavem, Portugal

[2] Univ Tecn Lisboa, Inst Super Tecn, Ctr Quim Estrutural, P-1049001 Lisbon, Portugal

[3] Univ Toulouse 3, Lab Chim & Phys Quant IRSAMC, F-31400 Toulouse, France

[4] CEA Grenoble, INAC, Lab Reconnaissance Ion & Chim Coordinat, Serv Chim Inorgan & Biol,CNRS FRE3200,UMR E CEA U, F-38054 Grenoble 09, France

来源：

DALTON TRANSACTIONS | 2013年 / 42卷 / 24期

关键词：

SINGLE-MOLECULE-MAGNET; N-DONOR LIGANDS; URANIUM(III) COMPLEX; TRIVALENT URANIUM; IODIDE COMPLEXES; F-ELEMENTS; U-N; CHEMISTRY; SERIES; ION;

D O I：

10.1039/c3dt50753j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The iodouranium(III) complex with two hydrotris(3,5-dimethylpyrazolyl)borate ligands is shown to adopt three closely related forms in the solid state. In addition to the previously reported structure for [U(Tp(Me2))(2)I], in which one of the pyrazolyl rings coordinates side-on to the U atom, another structure incorporating solvent molecules presents undistorted pyrazol rings, and a third one is the ionic compound [U(Tp(Me2))(2)]I. The implications of this structural diversity for the recently reported single ion magnet behaviour in this complex are discussed, namely on the basis of quantum chemistry calculations. The main effect of the bonding of the iodine atom to uranium is the increase of the size of the first coordination sphere and lowering of the symmetry of the molecule, resulting in a smaller crystal field splitting.

引用

收藏

页码：8861 / 8867

页数：7

相关论文

共 49 条

[1] SIR97:: a new tool for crystal structure determination and refinement [J].

Altomare, A ;

Burla, MC ;

Camalli, M ;

Cascarano, GL ;

Giacovazzo, C ;

Guagliardi, A ;

Moliterni, AGG ;

Polidori, G ;

Spagna, R .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1999, 32 :115-119

[2] Synthesis and characterization of uranium(III) compounds supported by the hydrotris(3,5-dimethyl-pyrazolyl)borate ligand:: Crystal structures of [U(TpMe2)2(X)] complexes (X = OC6H2-2,4,6-Me3, dmpz, Cl) [J].

Antunes, MA ;

Domingos, A ;

dos Santos, IC ;

Marques, N ;

Takats, J .

POLYHEDRON, 2005, 24 (18) :3038-3045

[3] Uranium(III) scorpionates:: Synthesis and structure of [(TPMe2)2U{N(C6H5)2}] and [(TpMe2)2U{N(SiMe3)2}] [J].

Antunes, MA ;

Ferrence, GM ;

Domingos, A ;

McDonald, R ;

Burns, CJ ;

Takats, J ;

Marques, N .

INORGANIC CHEMISTRY, 2004, 43 (21) :6640-6643

[4] [U(TpMe2)2(bipy)]+: A Cationic Uranium(III) Complex with Single-Molecule-Magnet Behavior [J].

Antunes, Maria A. ;

Pereira, Laura C. J. ;

Santos, Isabel C. ;

Mazzanti, Marinella ;

Marcalo, Joaquim ;

Almeida, Manuel .

INORGANIC CHEMISTRY, 2011, 50 (20) :9915-9917

[5] Electronic Structures of Highly Symmetrical Compounds of f Elements 44 [1]. First Parametric Analysis of the Absorption Spectrum of a Molecular Compound of Tervalent Uranium: Tris[hydrotris(1-pyrazolyl)borato]uranium(III) [J].

Apostolidis, Christos ;

Morgenstern, Alfred ;

Rebizant, Jean ;

Kanellakopulos, Basil ;

Walter, Olaf ;

Powietzka, Bernhard ;

Karbowiak, Miroslav ;

Reddmann, Hauke ;

Amberger, Hanns-Dieter .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2010, 636 (01) :201-208

[6] Software News and Update MOLCAS 7: The Next Generation [J].

Aquilante, Francesco ;

De Vico, Luca ;

Ferre, Nicolas ;

Ghigo, Giovanni ;

Malmqvist, Per-Ake ;

Neogrady, Pavel ;

Pedersen, Thomas Bondo ;

Pitonak, Michal ;

Reiher, Markus ;

Roos, Bjorn O. ;

Serrano-Andres, Luis ;

Urban, Miroslav ;

Veryazov, Valera ;

Lindh, Roland .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2010, 31 (01) :224-247

[7] Oxo-Functionalization and Reduction of the Uranyl Ion through Lanthanide-Element Bond Homolysis: Synthetic, Structural, and Bonding Analysis of a Series of Singly Reduced Uranyl-Rare Earth 5f1-4fnComplexes [J].

Arnold, Polly L. ;

Hollis, Emmalina ;

Nichol, Gary S. ;

Love, Jason B. ;

Griveau, Jean-Christophe ;

Caciuffo, Roberto ;

Magnani, Nicola ;

Maron, Laurent ;

Castro, Ludovic ;

Yahia, Ahmed ;

Odoh, Samuel O. ;

Schreckenbach, Georg .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (10) :3841-3854

[8] Modeling the properties of uranium-based single ion magnets [J].

Baldovi, Jose J. ;

Cardona-Serra, Salvador ;

Clemente-Juan, Juan M. ;

Coronado, Eugenio ;

Gaita-Arino, Alejandro .

CHEMICAL SCIENCE, 2013, 4 (03) :938-946

[9] The affinity and selectivity of terdentate nitrogen ligands towards trivalent lanthanide and uranium ions viewed from the crystal structures of the 1 : 3 complexes [J].

Berthet, JC ;

Miquel, Y ;

Iveson, PB ;

Nierlich, M ;

Thuéry, P ;

Madic, C ;

Ephritikhine, M .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (16) :3265-3272

[10] First characterization of an uranium(III) complex with a carbonyl-containing ligand:: Syntheses and X-ray crystal structures of the homoleptic dimethylformamide complexes [M(dmf)n]I3 (M = Ce, Nd and n=8; M = La, Ce, U and n=9) [J].

Berthet, Jean-Claude ;

Thuery, Pierre ;

Ephritikhine, Michel .

POLYHEDRON, 2006, 25 (07) :1700-1706

← 1 2 3 4 5 →