Structural studies of rare earth/transition metal complex ion systems as a basis for understanding their thermal decomposition to mixed oxides

被引:54
作者
Brayshaw, PA
Hall, AK
Harrison, WTA
Harrowfield, JM
Pearce, D
Shand, TM
Skelton, BW
Whitaker, CR
White, AH
机构
[1] Univ Western Australia, Res Ctr Adv Mineral & Mat Proc, Nedlands, WA 6009, Australia
[2] Univ Western Australia, Nedlands, WA 6907, Australia
[3] Univ Autonoma Barcelona, Inst Ciencia Mat Barcelona, Bellaterra 08193, Spain
关键词
dipicolinates; rare earths; crystal structures; mixed oxides; thermochemistry;
D O I
10.1002/ejic.200400863
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Thermal decomposition in air of the series of complexes [Co(NH3)(6)][Ln(dipic)(3)]center dot xH(2)O, [Cr(en)(3)][Ln(dipic)(3)]center dot yH(2)O and [Cr(urea)(6)][Ln(dipic)(3)]-zH(2)O (Ln = La - Lu, excluding Pm but plus Y; dipic = 2,6-pyridinedicarboxylate) to give oxide phases has been examined. The products were characterised by powder X-ray diffraction, magnetic and surface area measurements. From the Co-containing species, either Co3O4 + Ln(2)O(3) or perovskite (CoLnO(3)) products result, while the Cr-containing species provide CrLnO(4) phases in addition, the monazite form of CrNdO4 being detected for the first time in this way. Underpinning consideration of the solid state decomposition mechanisms, single-crystal X-ray structure determinations have been performed on [Co(NH3)(6)][Ln(dipic)(3)] nH(2)O across the Ln series, defining differing phases (all triclinic P (1) over bar) for n = 5 (encompassing Ln = La-Pr), n = 8(.5) (Ln = Tm - Eu) and n = 10 (Ln = Pr - Er, including Y), and also on one of the low-temperature decomposition products, [Co(NH3)(6)]Cl-dipic center dot 2H(2)O (1). The structure of 1 provides evidence that conventional pi-stacking of the dipicolinate anions may be of some importance in determining the solid state array, whereas consideration of all structures involving [Ln(dipic)(3)](3-) anions indicates that "edge-to-face" interactions between dipicolinate ligands of adjacent complex anions may also be determinants of the formation of sheetlike arrays of the trianions commonly observed in these compounds. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).
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页码:1127 / 1141
页数:15
相关论文
共 86 条
[1]   STRUCTURAL STUDIES ON RARE-EARTH CARBOXYLATES .12. CRYSTAL AND MOLECULAR STRUCTURE OF TRICLINIC TRISODIUM TRIS-(PYRIDINE-2,6-DICARBOXYLATO)NEODYMATE(III) 15-HYDRATE [J].
ALBERTSS.J .
ACTA CHEMICA SCANDINAVICA, 1972, 26 (03) :1023-&
[2]   STRUCTURAL STUDIES ON RARE EARTH CARBOXYLATES .4. CRYSTAL AND MOLECULAR STRUCTURE OF ORTHORHOMBIC TRISODIUM TRIS (PRIDINE-2,6-DICARBOXYLATO)YTTERBIUMATE(III)-14-HYDRATE [J].
ALBERTSS.J .
ACTA CHEMICA SCANDINAVICA, 1970, 24 (04) :1213-&
[3]   STRUCTURAL STUDIES ON RARE-EARTH CARBOXYLATES .10. CRYSTAL AND MOLECULAR STRUCTURE OF MONOCLINIC TRISODIUM TRIS-(PYRIDINE-2,6-DICARBOXYLATO)YTTERBATE (III) 13-HYDRATE [J].
ALBERTSSON, J .
ACTA CHEMICA SCANDINAVICA, 1972, 26 (03) :985-+
[4]   STRUCTURAL STUDIES ON RARE-EARTH CARBOXYLATES .11. CRYSTAL-STRUCTURE OF HEXAGONAL TRISODIUM TRIS (PYRIDINE-2,6-DICARBOXYLATO)YTTERBATE(III) MONO(SODIUM PERCHLORATE) DECAHYDRATE [J].
ALBERTSSON, J .
ACTA CHEMICA SCANDINAVICA, 1972, 26 (03) :1005-+
[5]   SOME NEUTRON-DIFFRACTION INVESTIGATIONS AT NUCLEAR CENTER OF GRENOBLE [J].
BERTAUT, EF ;
BASSI, G ;
BUISSON, G ;
BURLET, P ;
CHAPPERT, J ;
DELAPALME, A ;
MARESCHAL, J ;
ROULT, G ;
ALEONARD, R ;
PAUTHENET, R ;
REBOUILLAT, JP .
JOURNAL OF APPLIED PHYSICS, 1966, 37 (03) :1038-+
[6]  
BEVAN DJM, 1978, HDB CHEM PHYS RARE E, V3, pCH28
[7]   A STRONGLY LUMINESCENT ORGANIC-SOLVENT-SOLUBLE SALT OF THE TRIS(DIPICOLINATO)EUROPIUM(III) TRIANION [J].
BRAYSHAW, PA ;
HARROWFIELD, JM ;
SOBOLEV, AN .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1995, 51 :1799-1802
[8]   SYNTHETIC, STRUCTURAL, AND SPECTROSCOPIC STUDIES ON SOLIDS CONTAINING TRIS(DIPICOLINATO) RARE-EARTH ANIONS AND TRANSITION OR MAIN-GROUP METAL-CATIONS [J].
BRAYSHAW, PA ;
BUNZLI, JCG ;
FROIDEVAUX, P ;
HARROWFIELD, JM ;
KIM, Y ;
SOBOLEV, AN .
INORGANIC CHEMISTRY, 1995, 34 (08) :2068-2076
[9]  
BUISSON G, 1964, CR HEBD ACAD SCI, V259, P411
[10]   PHOTOPHYSICAL PROPERTIES OF LANTHANIDE DINUCLEAR COMPLEXES WITH P-TERT-BUTYLCALIX[8]ARENE [J].
BUNZLI, JCG ;
FROIDEVAUX, P ;
HARROWFIELD, JM .
INORGANIC CHEMISTRY, 1993, 32 (15) :3306-3311