Self-assembly of double and triple helices controlled by metal ion stereochemical preference

Piguet, Claude; Bérnardinelli, Gerald; Bocquet, Bernard; Quattropani, Anna; Williams, Alan F.

doi:10.1021/ja00045a016

Cited by 187 publications

(148 citation statements)

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“…Solvents were purified by a non-hazardous procedure by passing them onto activated alumina columns (Innovative Technology Inc. system; [35]). Previously reported syntheses include 4-hydroxy-pyridine-2,6-dicarboxylic acid diethyl ester 2 from chelidamic acid 1 (yield: 75%; [16,36]), 3,3 -dinitro-4,4 -bis (N-aminomethyl-diphenyl)methane 6 (yield: 75%) and 4,4 -methanediyl-bis(N-methylbenzene-1,2-diamine) 7 (yield: 85%) [16,22,37], H 2 L POEt [22], Et 2 L C2 and H 2 L C2 [17], the phthalimide-fitted arm 10 [26], as well as the bromination of 2-[2-(2-methoxy-ethoxy)-ethoxy]-ethanol with PBr 3 to yield arm 8 [38,39], see scheme 2 for the numbering of the compounds. (c) 4-Methoxy-pyridine-2,6-dicarboxylic acid diethyl ester (3) This synthesis was adapted from Horvath et al [40].…”

Section: Experimental Section (A) Starting Materials and General Procmentioning

confidence: 99%

Synthesis and cell localization of self-assembled dinuclear lanthanide bioprobes

Chauvin

Thomas

Song

et al. 2013

Phil. Trans. R. Soc. A.

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Section: Experimental Section (A) Starting Materials and General Procmentioning

confidence: 99%

Synthesis and cell localization of self-assembled dinuclear lanthanide bioprobes

Chauvin

Thomas

Song

et al. 2013

Phil. Trans. R. Soc. A.

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“…Repetitive ligand strands containing several bidentate subunits S, such as 2,2'-bipyridines (bipy), yield homostrand double-helical metal complexes with metal ions M of tetrahedral coordination geometry (2)(3)(4)(5)(6)(7). Ligand strands containing tridentate subunits, such as 2,2':6',2"-terpyridine (terpy), yield homostrand double helicates with metal ions of octahedral geometry (4,6,8,9).…”

mentioning

confidence: 99%

Self-assembly of a heteroduplex helicate from two different ligand strands and Cu(II) cations.

Hasenknopf¹,

Lehn²,

Baum³

et al. 1996

Proc. Natl. Acad. Sci. U.S.A.

163

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Cu(II) ions have been reacted with a 1/1 mixture of two linear ligands, one containing three 2,2'-bipyridine groups and the other three 2,2':6',2"-terpyridine groups. Absorption spectroscopy and fast atom bombardment mass spectrometry indicate the formation of a trinuclear complex containing one ligand of each kind. Determination of the crystal structure of this compound has confirmed that it is indeed a linear trinuclear complex in which two different ligands are wrapped in a helical fashion around the pentacoordinated metal ions. The central coordination geometry is trigonal bipyramidal; the two lateral Cu(II) ions are in a square pyramidal environment. Thus, a heteroduplex helicate is formed by the self-assembly of two different ligand strands and three specific metal ions induced by the coordination number and geometry of the latter. The self-assembly process may be considered to result from the reading of the steric and binding information present in the two ligands by Cu(II) ions through a pentacoordination algorithm. The same ligands have been shown earlier to yield homoduplex helicates from ions of tetrahedral and octahedral coordination geometry and strands of bidentate bipyridines and tridentate terpyridines, respectively. These two types of artificial double helical species may be related on one hand to the natural homoduplex nucleic acids and on the other hand to the DNA:RNA heteroduplex. Double helicates, multinuclear double-helical metal complexes, have recently been attracting considerable interest. The formation of these species from ligand strands and specific metal ions has been studied in detail because it is a prototype for supramolecular self-assembly processes and because of the special structural features of the resulting helicates (1, 2). In addition, the species have been considered as a model for the structural and dynamic features of the double helix of nucleic acids.Repetitive ligand strands containing several bidentate subunits S, such as 2,2'-bipyridines (bipy), yield homostrand double-helical metal complexes with metal ions M of tetrahedral coordination geometry (2-7). Ligand strands containing tridentate subunits, such as 2,2':6',2"-terpyridine (terpy), yield homostrand double helicates with metal ions of octahedral geometry (4,6,8,9). In these homoduplex helicates, two identical ligands wrap around the metal ions forming coordination centers MS2, which connect the two strands and hold the two S groups, one of each strand, in a more or less perpendicular orientation.Within the framework of programmed supramolecular systems (1), one may consider the formation of double helicates to result from the "reading" of the steric and binding information of the ligands by specific metal ions, following the algorithm defined by the coordination geometry of the metal ion.Of particular interest, both as a further step in the control of self-assembly through adequate programming and by the formation of a novel helicate species, would be the generation of a heteroduplex helicate from two ...

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“…These podands react with Fe 3+ to form a dinuclear complex having a triple-stranded helical structure, as determined by NMR measurements and circular dichroism spectroscopy 81,82 . It was shown in the last section that ligand 22 (Chart 3) reacts with Co 2+ to give a triple-stranded helicate 53 . Ligand 32 also yielded triple helix Co 2+ complexes 83 .…”

Section: Triple-stranded Helicatesmentioning

confidence: 99%

“…Ligand 32 also yielded triple helix Co 2+ complexes 83 . Interestingly, a subtle structural change between these ligands allowed the electrochemical oxidation of Co 2+ in the complex to Co 3+ , which was not possible to achieve in the complex formed with 22 53,83 . The resultant complex [Co 2 (32) 3 ] 6+ also has a triple helical structure.…”

Section: Triple-stranded Helicatesmentioning

confidence: 99%

“…Complexation of ligand 19 (two equivalents) with Fe 2+ and Cu + (one and two equivalents, respectively) in acetonitrile yields the homostranded Other different ligands have been employed in order to explore different levels of molecular programming leading to the formation of double helical structures (Chart 3) 32,52 . It has been shown that the multisite ligand 22 reacts with Cu + to give a double-stranded helicate while Co 2+ , able to perform an octahedral reading, yields a triple-stranded helicate 53 . Compound 23 is a versatile ligand that has been used to give different double-stranded helicates in the presence of Pd 2+ (54) or Cu 2+ (55) .…”

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confidence: 99%

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Self-assembly in self-organized inorganic systems: a view of programmed metallosupramolecular architectures

Machado¹,

Baxter²,

Lehn³

2001

J. Braz. Chem. Soc.

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Os avanços recentes das pesquisas na área de sistemas inorgânicos automontados são resumidos neste artigo de revisão, em especial aqueles envolvendo os metalo-helicatos, os metaloexorreceptores e as arquiteturas inorgânicas formadas a partir de componentes múltiplos. As aplicações, assim como as perspectivas vislumbradas para estes sistemas, são também discutidas.This review summarizes the recent advances that have been performed on self-assembled inorganic systems, especially on helical systems, metallo-exoreceptors and on architectures formed from multiple components. In addition, applications as well as the perspectives for these designed systems are also discussed.

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Self-assembly of double and triple helices controlled by metal ion stereochemical preference

Cited by 187 publications

References 0 publications

Synthesis and cell localization of self-assembled dinuclear lanthanide bioprobes

Synthesis and cell localization of self-assembled dinuclear lanthanide bioprobes

Self-assembly of a heteroduplex helicate from two different ligand strands and Cu(II) cations.

Self-assembly in self-organized inorganic systems: a view of programmed metallosupramolecular architectures

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