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Title: Self-assembly and photophysical properties of lanthanide dinuclear triple-helical complexes

Abstract

The dinucleating ligand bis[1-methyl-2-(6[prime]-[1[double prime]-(3,5-dimethoxybenzyl)benzimidazol-2[double prime]-yl]pyrid-2[prime]-yl)benzimidazol-5-yl]methane (L) reacts with lanthanide perchlorates to give dinuclear 2:3 complexes [Ln[sub 2](L)[sub 3]][sup 6+] (Ln = La, Eu, Gd, Tb, and Lu). Detailed ES-MS, [sup 1]H-NMR, luminescence, and spectrophotometric measurements in acetonitrile show that the cations [Ln[sub 2](L)[sub 3]][sup 6+] are produced by strict self-assembly and adopt a triple-helical structure in solution (pseudo-D[sub 3] symmetry). The crystal structure of [Eu[sub 2](L,)[sub 3]](CIO[sub 4])[sub 6](CH[sub 3]CN)[sub 9] (11, Eu[sub 2]C[sub 195]H[sub 177]N[sub 39]O[sub 36]Cl[sub 6], a = 17.634-(3) [angstrom], b = 21.408(4) [angstrom], c = 29.437(7) [angstrom], [alpha] = 82.13(1)[degree], [beta] = 85.76(1)[degree], [gamma] = 89.79(1)[degree], triclinic, Pl, Z = 2) shows a dinuclear pseudo-D[sub 3] triple-helical cation, [Eu[sub 2](L)[sub 3]][sup 6+], where the three bis(terdentate) ligands L are wrapped around the helical axis defined by the europium atoms. The Eu(III) of each site is 9-coordinated by six nitrogen atoms of the benzimidazole units occupying the vertices and three nitrogen atoms of the pyridine units occupying the capping positions of a slightly distorted, tricapped trigonal prism. Luminescence studies of the crystalline complex [Eu[sub 2](L)[sub 3]]-(ClO[sub 4])[sub 6][center dot]nsolv (n = 9, solv = CH[sub 3]CN, 11; n = 2, solv = H[sub 2]O, 6; nmore » = 9, solv = H[sub 2]O, 7) confirm the pseudo-D[sub 3] symmetry of the Eu(III) sites in 11 and show that secondary interactions with water molecules in 6 and 7 destroy the trigonal symmetry. 46 refs., 7 figs., 6 tabs.« less

Authors:
; ;  [1];  [2];  [3]
  1. Univ. of Geneva (Switzerland)
  2. Univ. of Lausanne (Switzerland)
  3. Hoffmann-La Roche, Basel (Switzerland)
Publication Date:
OSTI Identifier:
5146699
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (United States)
Additional Journal Information:
Journal Volume: 115:18; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; RARE EARTH COMPLEXES; OPTICAL PROPERTIES; PHYSICAL PROPERTIES; STABILITY; SYNTHESIS; CRYSTAL STRUCTURE; ENERGY TRANSFER; EUROPIUM COMPLEXES; EXCITED STATES; GADOLINIUM COMPLEXES; LANTHANUM COMPLEXES; LIGANDS; LUMINESCENCE; LUTETIUM COMPLEXES; MASS SPECTROSCOPY; MOLECULAR STRUCTURE; NMR SPECTRA; SPECTROPHOTOMETRY; STOICHIOMETRY; TERBIUM COMPLEXES; COMPLEXES; ENERGY LEVELS; SPECTRA; SPECTROSCOPY; 400201* - Chemical & Physicochemical Properties; 400500 - Photochemistry

Citation Formats

Piguet, C, Bernardinelli, G, Williams, A F, Buenzli, J C.G., and Hopfgartner, G. Self-assembly and photophysical properties of lanthanide dinuclear triple-helical complexes. United States: N. p., 1993. Web. doi:10.1021/ja00071a032.
Piguet, C, Bernardinelli, G, Williams, A F, Buenzli, J C.G., & Hopfgartner, G. Self-assembly and photophysical properties of lanthanide dinuclear triple-helical complexes. United States. https://doi.org/10.1021/ja00071a032
Piguet, C, Bernardinelli, G, Williams, A F, Buenzli, J C.G., and Hopfgartner, G. Wed . "Self-assembly and photophysical properties of lanthanide dinuclear triple-helical complexes". United States. https://doi.org/10.1021/ja00071a032.
@article{osti_5146699,
title = {Self-assembly and photophysical properties of lanthanide dinuclear triple-helical complexes},
author = {Piguet, C and Bernardinelli, G and Williams, A F and Buenzli, J C.G. and Hopfgartner, G},
abstractNote = {The dinucleating ligand bis[1-methyl-2-(6[prime]-[1[double prime]-(3,5-dimethoxybenzyl)benzimidazol-2[double prime]-yl]pyrid-2[prime]-yl)benzimidazol-5-yl]methane (L) reacts with lanthanide perchlorates to give dinuclear 2:3 complexes [Ln[sub 2](L)[sub 3]][sup 6+] (Ln = La, Eu, Gd, Tb, and Lu). Detailed ES-MS, [sup 1]H-NMR, luminescence, and spectrophotometric measurements in acetonitrile show that the cations [Ln[sub 2](L)[sub 3]][sup 6+] are produced by strict self-assembly and adopt a triple-helical structure in solution (pseudo-D[sub 3] symmetry). The crystal structure of [Eu[sub 2](L,)[sub 3]](CIO[sub 4])[sub 6](CH[sub 3]CN)[sub 9] (11, Eu[sub 2]C[sub 195]H[sub 177]N[sub 39]O[sub 36]Cl[sub 6], a = 17.634-(3) [angstrom], b = 21.408(4) [angstrom], c = 29.437(7) [angstrom], [alpha] = 82.13(1)[degree], [beta] = 85.76(1)[degree], [gamma] = 89.79(1)[degree], triclinic, Pl, Z = 2) shows a dinuclear pseudo-D[sub 3] triple-helical cation, [Eu[sub 2](L)[sub 3]][sup 6+], where the three bis(terdentate) ligands L are wrapped around the helical axis defined by the europium atoms. The Eu(III) of each site is 9-coordinated by six nitrogen atoms of the benzimidazole units occupying the vertices and three nitrogen atoms of the pyridine units occupying the capping positions of a slightly distorted, tricapped trigonal prism. Luminescence studies of the crystalline complex [Eu[sub 2](L)[sub 3]]-(ClO[sub 4])[sub 6][center dot]nsolv (n = 9, solv = CH[sub 3]CN, 11; n = 2, solv = H[sub 2]O, 6; n = 9, solv = H[sub 2]O, 7) confirm the pseudo-D[sub 3] symmetry of the Eu(III) sites in 11 and show that secondary interactions with water molecules in 6 and 7 destroy the trigonal symmetry. 46 refs., 7 figs., 6 tabs.},
doi = {10.1021/ja00071a032},
url = {https://www.osti.gov/biblio/5146699}, journal = {Journal of the American Chemical Society; (United States)},
issn = {0002-7863},
number = ,
volume = 115:18,
place = {United States},
year = {1993},
month = {9}
}