Self-assembly of metallosupramolecular rhombi from chiral concave 9,9'-spirobifluorene-derived bis(pyridine) ligands.

Two new 9,9’-spirobifluorene-based bis(4-pyridines) were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp)2M2L2] rhombi with cis-protected [(dppp)Pd]2+ and [(dppp)Pt]2+ ions. The self-assembly process of the racemic ligand preferably occurs in a narcissistic self-recognising manner. Hence, a mixture of all three possible stereoisomers [(dppp)2M2{(R)-L}2](OTf)4, [(dppp)2M2{(S)-L}2](OTf)4, and [(dppp)2M2{(R)-L}{(S)-L}](OTf)4 was obtained in an approximate 1.5:1.5:1 ratio which corresponds to an amplification of the homochiral assemblies by a factor of approximately three as evidenced by NMR spectroscopy and m…

Chiral Self‐Sorting of trans ‐Chelating Chiral Ligands upon Formation of Pd II Complexes (Eur. J. Inorg. Chem. 15/2014)

Enantiomerically pure trinuclear helicates via diastereoselective self-assembly and characterization of their redox chemistry.

A tris(bipyridine) ligand 1 with two BINOL (BINOL = 2, 2′-dihydroxy-1, 1′-binaphthyl) groups has been prepared in two enantiomerically pure forms. This ligand undergoes completely diastereoselective self-assembly into D2-symmeteric double-stranded trinuclear helicates upon coordination to copper(I) and silver(I) ions and to D3-symmetric triple-stranded trinuclear helicates upon coordination to copper(II), zinc(II), and iron(II) ions as demonstrated by mass spectrometry, NMR and CD spectroscopy in combination with quantum chemical calculations and X-ray diffraction analysis. According to the calculations, the single diastereomers that are formed during the self-assembly process are strongly …

Unexpected self-assembly of a homochiral metallosupramolecular M4L4 catenane

Two enantiomerically pure 9,9'-spirobifluorene-based bis(pyridine) ligands 1 and 2 were prepared to study their self-assembly behavior upon coordination to cis-protected palladium(II) ions. Whereas the sterically more demanding ligand, 2, gave rise to the expected dinuclear metallosupramolecular M2L2 rhombi, the sterically less demanding ligand, 1, acts as a template to give rise to a homochiral metallosupramolecular M4L4 catenane.

Chiral Self-Sorting of trans-Chelating Chiral Ligands upon Formation of PdII Complexes

Invited for the cover of this issue is the group of Arne Lutzen at the University of Bonn, Germany. The cover image shows two dissymmetric bis(3-pyridyl) ligands based on a planar chiral pseudo-ortho-disubstituted [2.2]paracyclophane scaffold. Upon forming a mononuclear [ML2] complex with palladium(II) ions, these ligands act in a trans-chelating manner and undergo complete chiral self-sorting.

CCDC 986176: Experimental Crystal Structure Determination

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CCDC 986175: Experimental Crystal Structure Determination

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CCDC 986177: Experimental Crystal Structure Determination

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CCDC 1003004: Experimental Crystal Structure Determination

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CCDC 999739: Experimental Crystal Structure Determination

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CCDC 986178: Experimental Crystal Structure Determination

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CCDC 971933: Experimental Crystal Structure Determination

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