Synthesis and crystal structure of 1:2 mixed uranyl/alkali metal ions (Li+, Na+, K+, Cs+) complexes of p-tert-butyltetrahomodioxacalix[4]arene

被引:50
作者
Thuéry, P
Masci, B
机构
[1] CEA Saclay, DSM DRECAM SCM, CNRS URA 331, F-91191 Gif Sur Yvette, France
[2] Univ Roma La Sapienza, Dipartimento Chim, I-00185 Rome, Italy
关键词
D O I
10.1039/b302233a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
p-tert-Butyltetrahomodioxacalix[4] arene LH4 reacts with uranyl nitrate hexahydrate in the presence of alkali metal hydroxides to give mixed complexes containing the same [UO2(L)](2-) central core. All alkali metal ions are bound to the basic uranyl oxo groups, which act as mono- (Li+, Na+) or bidentate (K+, Cs+) ligands. The resulting structures largely depend on the size and predominantly "hard" or "soft" character of the alkali metal ion. Li+ and Na+ are coordinated in both "endo" and "exo" modes, Li+ giving a monomer with one cation bound to each oxo group and Na+ a dimer with a bridging, oxo-coordinated, Na-2(CH3OH)(8) moiety. Both K+ and Cs+ give polymeric chains, with two cations in the macrocycle cavity, involved in cation-pi interactions with the aromatic rings and bound to the oxo groups from two neighbouring molecules in the chain, with differences in further coordination to the calixarenes which are related to the softer nature of Cs+. Unprecedented supramolecular architectures based on coordination bonds are thus obtained.
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页码:2411 / 2417
页数:7
相关论文
共 35 条
[1]   The Cambridge Structural Database: a quarter of a million crystal structures and rising [J].
Allen, FH .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 2002, 58 (3 PART 1) :380-388
[2]  
[Anonymous], 1999, SHELXTL VERSION 5 1
[3]  
ARNAUDNEU F, 2001, CALIXARENES 2001, pCH35
[4]   Calixarenes as polyhapto-aromatic ligands:: Alkali metal ions and sulfonated calixarenes [J].
Asfari, Z ;
Harrowfield, J ;
Thuéry, P ;
Vicens, J .
SUPRAMOLECULAR CHEMISTRY, 2003, 15 (01) :69-77
[5]   ALKALI-METAL ION COMPLEXES OF THE CALIXARENES .1. CESIUM BONDING IN CALIX[4]ARENE SYSTEMS [J].
ASSMUS, R ;
BOHMER, V ;
HARROWFIELD, JM ;
OGDEN, MI ;
RICHMOND, WR ;
SKELTON, BW ;
WHITE, AH .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1993, (16) :2427-2433
[6]   SYNTHESIS OF NEUTRAL AND ANIONIC URANYL ARYLOXIDE COMPLEXES FROM URANYL AMIDE PRECURSORS - X-RAY CRYSTAL-STRUCTURES OF UO2(O-2,6-I-PR2C6H3)(2)(PY)(3) AND [NA(THF)(3)](2)[UO2(O-2,6-ME(2)C(6)H(3))(4)] [J].
BARNHART, DM ;
BURNS, CJ ;
SAUER, NN ;
WATKIN, JG .
INORGANIC CHEMISTRY, 1995, 34 (16) :4079-4084
[7]   Aqueous reactions of U(VI) at high chloride concentrations: Syntheses and structures of new uranyl chloride polymers [J].
Bean, AC ;
Xu, YW ;
Danis, JA ;
Albrecht-Schmitt, TE ;
Scott, BL ;
Runde, W .
INORGANIC CHEMISTRY, 2002, 41 (25) :6775-6779
[8]   Systematic structural coordination chemistry of p-tert-butyltetrathiacalix[4]arene:: 1.: Group 1 elements and congeners [J].
Bilyk, A ;
Hall, AK ;
Harrowfield, JM ;
Hosseini, MW ;
Skelton, BW ;
White, AH .
INORGANIC CHEMISTRY, 2001, 40 (04) :672-686
[9]   A trigonal bipyramidal uranyl amido complex:: Synthesis and structural characterization of [Na(THF)2] [UO2(N(SiMe3)2)3] [J].
Burns, CJ ;
Clark, DL ;
Donohoe, RJ ;
Duval, PB ;
Scott, BL ;
Tait, CD .
INORGANIC CHEMISTRY, 2000, 39 (24) :5464-5468
[10]  
CASNATI A, 2001, CALIXARENES 2001, pCH20