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.

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 preferred compared to the next stable diastereomers. Due to this strong preference, the self-assembly of the helicates from racemic 1 proceeds in a completely narcissistic self-sorting manner with an extraordinary high degree of self-sorting that proves the power and reliability of this approach to achieve high-fidelity diastereoselective self-assembly via chiral self-sorting to get access to stereochemically well-defined nanoscaled objects. Furthermore, mass spectrometric methods including electron capture dissociation MS(n) experiments could be used to elucidate the redox behavior of the copper helicates.

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 mass spectrometry. The racemic homochiral assemblies could also be characterised by single crystal X-ray diffraction.

Enantiomerically pure [M(6)L(12)] or [M(12)L(24)] polyhedra from flexible bis(pyridine) ligands.

Coordination-driven self-assembly is one of the most powerful strategies to prepare nanometer-sized discrete (supra)molecular assemblies. Herein, we report on the use of two constitutionally isomeric BINOL-based bis(pyridine) ligands for this purpose. Upon coordination to Pd(II) ions these self-assemble into enantiomerically pure endo- and exo-functionalized hexa- and dodecanuclear metallosupramolecular spheres with a chiral skeleton depending on the substitution pattern of the BINOL core. These aggregates were characterized by NMR, MS, DLS, TEM, and EELS as well as ECD. Furthermore, experimental ECD data could be compared to those obtained from theoretical simulations using a simplified Tamm-Dancoff approximation to time-dependent DFT to rationalize the extraordinary high molar circular dichroisms. Despite the rotational freedom around the central aryl-aryl bond of these ligands, the self-assembly process happens completely selective in a "narcissistic" self-recognition manner.

Homochiral supramolecular M2L4 cages by high-fidelity self-sorting of chiral ligands.

A 1,1'-binaphthyl-based bis(pyridine) ligand (1) was prepared in racemic and enantiomerically pure form to study the formation of [Pd2(1)4] complexes upon coordination to palladium(II) ions with regard to the degree of chiral self-sorting. The self-assembly process proceeds in a highly selective narcissistic self-recognition manner to give only homochiral supramolecular M2 L4 cages, which were characterized by ESI-MS, NMR, and electronic circular dichroism (ECD) spectroscopy, as well as by single-crystal XRD analysis.

Equipping metallo-supramolecular macrocycles with functional groups: assemblies of pyridine-substituted urea ligands.

A series of di-(m-pyridyl)-urea ligands were prepared and characterized with respect to their conformations by NOESY experiments and crystallography. Methyl substitution in different positions of the pyridine rings provides control over the position of the pyridine N atoms relative to the urea carbonyl group. The ligands were used to self-assemble metallo-supramolecular M(2)L(2) and M(3)L(3) macrocycles which are generated in a finely balanced equilibrium in DMSO and DMF according to DOSY NMR experiments and ESI FTICR mass spectrometry. Again, crystallography was used to characterize the assemblies. Methyl substitution in positions next to the pyridine nitrogen prevents coordination, while the other ligands form small metallo-supramolecular macrocycles. The incorporated urea carbonyl groups provide hydrogen bonding sites which converge towards the center of the assemblies.

Surprising substituent effects on the self-assembly of helicates from bis(bipyridyl) BINOL ligands.

A number of different bis(bipyridyl) BINOL ligands were prepared using a convergent building block approach. These were studied with regard to their ability to undergo self-assembly to dinuclear helicates upon coordination to suitable late-transition-metal ions. Surprisingly, the substituents at the periphery of the ligand structure were found to have a marked influence on the outcome of the self-assembly processes with regard to the helicates composition, the stereoselectivity of the helicate formation, their redox reactivity, and their electronical properties as scrutinized by NMR- and CD-spectroscopic methods as well as ESI-mass spectrometric methods.

Basis Set Superposition Error along the Free-Energy Surface of the Water Dimer.

In this article we review the behavior of static plane wave basis set calculations in comparison to Gaussian basis set calculations. This was done in the framework of density functional theory for description of hydrogen bonds with the water dimer as an example. Furthermore we carried out molecular dynamics simulations enforcing the self-dissociation reaction of the water dimer to study the influence of the basis set onto the reaction. Not surprisingly, we find strongly varying results of the calculated forces for a chosen cutoff along the reaction coordinates. The basis set superposition errors of the dimer interaction energy are analyzed along the free-energy surface, i.e., along the trajectories. Based on the analysis along the trajectories a qualitative and quantitative estimate depending on the particular point of the free-energy surface can be provided. Namely, at the intermolecular O···H distance close to the equilibrium geometry the errors are smaller than at shorter O···H distances. However, the distribution at the equilibrium distance is more unsymmetrical than the distribution at short distances. It is wider, and the standard deviation is larger than at shorter distances where the basis set superposition error is larger.