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dc.contributor.authorKhutia, A.-
dc.contributor.authorSanz Miguel, Pablo J.-
dc.contributor.authorLippert, B.-
dc.identifierdoi: 10.1002/chem.201002722-
dc.identifierissn: 0947-6539-
dc.identifiere-issn: 1521-3765-
dc.identifier.citationChemistry - A European Journal 17(15): 4195-4204 (2011)-
dc.description.abstractPyrimidine (pym) ligands with their two endocyclic N-donor atoms provide 120° angles for molecular constructs, which, with the 90° angle metal fragments cis-a2MII (M=Pt, Pd; a=NH3 or a 2=diamine), form cyclic complexes known as metallacalix[n]arenes (with n=3, 4, 6, 8, ...). The number of possible isomers of these species depends on the symmetry of the pym ligand. Although highly symmetrical (C 2v) pym ligands form a single linkage isomer for any n and can adopt different conformations (e.g., cone, partial cone, 1,3-alternate, and 1,2-alternate in the case of n=4), low-symmetry pym ligands (Cs) can produce a higher number of linkage isomers (e.g., four in the case of n=4) and a large number of different conformers. In the absence of any self-sorting bias, the number of possible species derived from a self-assembly process between cis-a2MII and a Cs-symmetrical pym ligand can thus be very high. By using the Cs-symmetric pym nucleobase cytosine, we have demonstrated that the number of feasible isomers for n=4 can be reduced to one by applying preformed building blocks such as cis-[a 2M(cytosine-N3)2]n+ or cis-[a 2M(cytosinate-N1)2] (for the latter, see the accompanying paper: A. Khutia, P. J. Sanz Miguel, B. Lippert, Chem. Eur. J. 2011, 17, DOI: 10.1002/chem.2010002723) and treating them with additional cis-a 2MII. Moreover, intramolecular hydrogen-bonding interactions between the O2 and N4H2 sites of the cytosine ligands reduce the number of possible rotamers to one. This approach of the >directed> assembly of a defined metallacalix[4]arene is demonstrated.-
dc.description.sponsorshipThis work was supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, and the International Max Planck Research School in Chemical Biology in Dortmund (fellowship for A.K.).-
dc.title“Directed” Assembly of Metallacalix[n]arenes with Pyrimidine Nucleobase Ligands of Low Symmetry: Metallacalix[n]arene Derivatives of cis-[a2M(cytosine-N3)2]2+ (M=PtII, PdII; n=4 and 6)-
dc.description.versionPeer Reviewed-
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