STRUCTURAL AND PHOTOPHYSICAL PROPERTIES OF LANTHANIDE COMPLEXES WITH PLANAR AROMATIC TRIDENTATE NITROGEN LIGANDS AS LUMINESCENT BUILDING-BLOCKS FOR TRIPLE-HELICAL STRUCTURES

被引:127
作者
PIGUET, C
WILLIAMS, AF
BERNARDINELLI, G
BUNZLI, JCG
机构
[1] UNIV LAUSANNE,INST ANALYT & INORGAN CHEM,CH-1005 LAUSANNE,SWITZERLAND
[2] UNIV GENEVA,XRAY CRYSTALLOG LAB,CH-1211 GENEVA 4,SWITZERLAND
关键词
D O I
10.1021/ic00071a029
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The ligand 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (mbzimpy, 1) reacts with lanthanide perchlorate in acetonitrile to give the successive complexes [Ln(mbzimpy)n]3+ (n = 1-3). Tris complexes were isolated for La, Eu, Gd, and Tb, while a bis complex only could be crystallized for Lu. The crystal structure of [Lu(mbzimpy)2(H2O)(CH3-OH)] (ClO4)3.3CH3OH (12, LuC46H52N10O17Cl3, a = 13.140(3) angstrom, b = 22.007(4) angstrom, c = 18.927(7) angstrom, beta = 107.53(1)-degrees, monoclinic, P2(1)/c, Z = 4) shows three uncoordinated ClO4- anions and a [Lu(mbzimpy)2(H2O)(CH3OH)]3+ cation where Lu(III) is eight-coordinated by two meridional tridentate mbzimpy ligands, one methanol molecule, and one water molecule, leading to a low-symmetry coordination sphere around the metal ion. The crystal structure of [Eu(mbzimpy)3](ClO4)3 [6, EuC63H51N15O12Cl3, a = 24.703(2) angstrom, c = 16.982(2) angstrom, trigonal, R3BAR, Z = 6) shows a mononuclear cation [Eu(mbzimpy)3]3+ with C3 symmetry where Eu(III) is nine-coordinated by three tridentate mbzimpy (1) which are wrapped around the metal ion to give an approximate trigonal tricapped prismatic arrangement of the nine nitrogen donor atoms leading to a pseudo-D3 symmetry. Luminescence studies of crystalline [Eu(mbzimpy)3] (ClO4)3 (6) confirm the high symmetry for the Eu(III) sites while H-1-NMR and luminescence measurements in solution indicate that the triple-helical structure of [Eu(mbzimpy)3]3+ is maintained in acetonitrile. Spectrophotometric titrations show that the three expected successive complexes [Ln(mbzimpy)]3+, [Ln(mbzimpy)2]3+, and [Ln(mbzimpy)3]3+ are formed in solution for all the lanthanide ions studied (Ln = La, Nd, Eu, Gd, Tb, Ho, Yb, Lu), but that [Ln(mbzimpy)3]3+ complexes are significantly less stable for the heavier lanthanides (Ln = Ho, Yb, Lu) and for the tridentate ligands 2,6-bis(1-X-benzimidazol-2-yl)pyridine (X = propyl, pbzimpy, 2; X = 3,5-dimethoxybenzyl, dmbbzimpy, 3] which have bulky groups bound to the aromatic benzimidazole rings. The origin of these effects is discussed together with the use of these complexes as luminescent building blocks for the formation of triple-helical structures.
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页码:4139 / 4149
页数:11
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共 62 条
  • [1] ENERGY-TRANSFER LUMINESCENCE OF EUROPIUM(III) AND TERBIUM(III) CRYPTATES OF MACROBICYCLIC POLYPYRIDINE LIGANDS
    ALPHA, B
    LEHN, JM
    MATHIS, G
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1987, 26 (03): : 266 - 267
  • [2] LUMINESCENCE PROBES - THE EU-3+-CRYPTATES AND TB-3+-CRYPTATES OF POLYPYRIDINE MACROBICYCLIC LIGANDS
    ALPHA, B
    BALZANI, V
    LEHN, JM
    PERATHONER, S
    SABBATINI, N
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1987, 26 (12): : 1266 - 1267
  • [3] DYNAMICS OF ENERGY-TRANSFER IN TB1-XEUXP5O14 CRYSTALS
    ANH, TK
    STREK, W
    [J]. JOURNAL OF LUMINESCENCE, 1988, 42 (04) : 205 - 210
  • [4] [Anonymous], 1974, INT TABLES XRAY CRYS, VIV
  • [5] LUMINESCENCE PROPERTIES OF EU3+ AND TB3+ COMPLEXES OF BRANCHED MACROCYCLIC LIGANDS CONTAINING 4 2,2'-BIPYRIDINE UNITS
    BALZANI, V
    LEHN, JM
    VANDELOOSDRECHT, J
    MECATI, A
    SABBATINI, N
    ZIESSEL, R
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (02): : 190 - 191
  • [6] LUMINESCENCE PROPERTIES OF EU-3+ COMPLEXES OF TRIPODE AND TETRAPODE LIGANDS CONTAINING 2,2'-BIPYRIDINE UNITS
    BALZANI, V
    BERGHMANS, E
    LEHN, JM
    SABBATINI, N
    TERORDE, R
    ZIESSEL, R
    [J]. HELVETICA CHIMICA ACTA, 1990, 73 (08) : 2083 - 2089
  • [7] BALZANI V, 1992, PERSPECTIVES COORDIN, P153
  • [8] MOLECULAR HELICITY IN INORGANIC COMPLEXES - DOUBLE HELICAL BINUCLEAR COMPLEXES OF 2,2'-6',2''-6'',2'''-6''',2''''-QUINQUEPYRIDINE (L) - CRYSTAL-STRUCTURES OF [CU2L2(O2CME)][PF6]3.H2O AND [CU2L2][PF6]3.2MECN
    BARLEY, M
    CONSTABLE, EC
    CORR, SA
    MCQUEEN, RCS
    NUTKINS, JC
    WARD, MD
    DREW, MGB
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1988, (10): : 2655 - 2662
  • [9] STRUCTURE OF [2,6-BIS(2-BENZIMIDAZOLYL)PYRIDINE]DICHLOROCOPPER(II) DIMETHYLFORMAMIDE
    BERNARDINELLI, G
    HOPFGARTNER, G
    WILLIAMS, AF
    [J]. ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1990, 46 : 1642 - 1645
  • [10] BERNARDINELLI G, 1992, ANGEW CHEM INT EDIT, V31, P1629