Its information content is infinitely smaller than that of DNA, but its structure (see picture) ressembles the double-stranded helix produced by nature. This self-assembled, configurationally predetermined coordination polymer is built up from enantiopure chiral bipyridine-type ligands and silver ions.
Two tetradentate bispinene-bipyridine type ligands, each with six stereogenic carbon centers, were synthesized from (-)-alpha-pinene. Their ability to predetermine chiral configurations at metal centers was studied. The two diastereoisomers, L1 and L2, differ in their absolute configuration at the bridgehead position. These ligands form metal complexes with Ag(I), Pd(II), Zn(II), Cu(II), and Cd(II), with coordination numbers four, five, and six and with complete control of chirality at the metal centers. Using L1 rather than L2 leads to complexes of inverted absolute configuration at the metal centers. These diastereomeric coordination species can be obtained either as separate compounds or, in some cases, as solids containing them in a 1:1 ratio. Ligands L1 and L2 thus show that the pinene-bipyridines are versatile molecules for the formation of metal complexes with predetermined chirality. In all cases, absolute configurations were determined in the solid state by X-ray diffraction methods and in solution by CD spectroscopy. The sign of exciton couplets from the pi-pi* transitions always agrees with the expectations for a given local configuration at the metal center. The five-coordinate, inherently chiral species of Zn(II) and Cu(II) described in this article are the first examples of trigonal-bipyramidal metal complexes with predetermined absolute configuration containing topologically linear ligands.
A synthetic protocol involving the Friedländer reaction of 8-amino-7-quinolinecarbaldehyde followed by potassium dichromate oxidation was applied to 2,3,4-pentanetrione-3-oxime and 1-(pyrid-2'-yl)propane-1,2-dione-1-oxime to provide the ligands di-(phenathrolin-2-yl)-methanone (1) and phenanthrolin-2-yl-pyrid-2-yl-methanone (8), respectively. Ligand 1 complexed as a planar tetradentate with Pd(II) to form [Pd(1)](BF4)2 and with Ru(II) and two 4-substituted pyridines (4-R-py) to form [Ru(1)(4-R-py)2](PF6)2 where R = CF3, CH3, and Me2N. With [Ru(bpy)2Cl2], the dinuclear complex [(bpy)2Ru(1)Ru(bpy)2](PF6)4 was formed (bpy = 2,2'-bipyridine). Ligand 8 afforded the homoleptic Ru(II) complex [Ru(8)2](PF6)2, as well as the heteroleptic complex [Ru(8)(tpy)](PF6)2 (tpy = 2,2';6,2''-terpyridine). The ligands and complexes were characterized by their NMR and IR spectra, as well as an X-ray structure determination of [Ru(1)(4-CH3-py)2](PF6)2. Electrochemical analysis indicated metal-based oxidation and ligand-based reduction that was consistent with results from electronic absorption spectra. The complexes [Ru(1)(4-R-py)2](PF6)2 were sensitive to the 4-substituent on the axial pyridine: electron donor groups facilitated the oxidation while electron-withdrawing groups impeded it.
The hexadentate, and ditopic ligand 2,5-bis([2,2']bipyridin-6-yl)pyrazine yields a chiral, tetrameric, square shaped, self-assembled species upon complexation with Fe 2+ -ions. The racemate of this complex was resolved with antimonyl tatrate as chiral auxiliary. The purity of the enantiomer was determined by NMR spectroscopy, using a chiral, diamagnetic shift reagent, as well as by circular dichroism (CD). The CD-spectrum was also calculated by time dependent density functional theory, and the correlation that was found between CD spectrum and configuration was confirmed by X-ray cristallography. When a "chiralised" version of the ligand was used instead, the corresponding iron complex was obtained in diastereomerically pure form.
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