Arne Lützen

Mass Spectrometric Characterization and Gas-Phase Chemistry of Self-Assembling Supramolecular Squares and Triangles

A detailed mass spectrometric characterization of self-assembling polynuclear metal complexes is described. The complexes can only be ionized as intact species under a surprisingly narrow range of conditions by electrospray ionization. Comparison with the results from NMR experiments shows that several solution-phase features of these squares and triangles (such as trends in bond energies, ligand-exchange reactions, or square-triangle equilibria) are qualitatively reflected in the gas-phase data. Consequently, mass spectrometry represents a valuable method for the characterization of these compounds. Nevertheless, the formation of unspecific aggregates during the ionization process occurs and its implications are discussed. Beyond the chemistry in solution, the fragmentation pathways of these complexes in the gas phase have been studied by infrared multiphoton dissociation (IRMPD) experiments. The results of IRMPD studies allow us to draw conclusions with respect to the structure and energetics of fragmentation products. In this tandem MS experiment, reaction pathways can be observed directly which can hardly be analyzed in solution. According to these results, the equilibration of triangles and squares involves the supramolecular analogue of a neighboring-group effect.

Organic Molecular Nanotechnology

A new route to bottom-up organic nanotechnology is presented. Molecular building blocks with specific optoelectronic properties are designed and grown via directed self-assembly arrays of morphologically controlled light-emitting organic nanofibers on template surfaces. The fibers can be easily transferred from the growth substrate to device platforms either as single entities or as ordered arrays. Due to the extraordinary flexibility in the design of their optoelectronic properties they serve as key elements in next-generation nanophotonic devices.

Artificial Allosteric Receptors

Cooperative effects in the binding of two or more substrates to different binding sites of a receptor that are a result of a conformational change caused by the binding of the first substrate--also referred to as the effector--are called allosteric effects. In biological systems, allosteric regulation is a widely used mechanism to control the function of proteins and enzymes in cellular metabolism. Inspired by this a lot of efforts have been made in supramolecular chemistry to implement this concept into artificial systems to control functions as molecular recognition, signal amplification, or even reactivity and catalysis. This review gives an up-to-date overview over the different approaches that have been reported ever since the first examples from the late 1970s/early 1980s. It covers both homo- and heterotropic examples and is divided according to the nature of the effector--cationic, anionic, or neutral--effectors and systems that use combinations of those.

Self‐Discriminating Self‐Assembly of Dinuclear Heterochiral Rhombs from Tröger’s Base Derived Bis(pyridyl) Ligands

Five racemic dissymmetric bis(pyridyl) ligands based on 2,8- or 3,9-difunctionalised Trögers base derivatives have been synthesised. Only those derived from a 2,8-difunctionalised scaffold were found to undergo selective self-assembly to discrete self-assembled dinuclear metallosupramolecular aggregates of rhomboid shape upon coordination to cis-protected Pd(2+) or Pt(2+) ions, as evidenced by ESI mass spectrometry, NMR spectroscopy and single-crystal X-ray diffraction. Interestingly, these processes were found to be highly diastereoselective leading to the formation of C(2v)-symmetric heterochiral assemblies in a self-discriminating manner.

A New Structural Motif for an Enantiomerically Pure Metallosupramolecular Pd4L8 Aggregate by Anion Templating

An enantiomerically pure BINOL-based bis(3-pyridyl) ligand 1 assembles into a homochiral [Pd4(1)8] complex upon coordination to tetravalent Pd(II) ions. The formation of this aggregate is templated by two tetrafluoroborate counterions that are encapsulated in two peripheral cavities. The resulting structure is a new structural motif for this kind of metallosupramolecular assemblies that arranges the palladium ions in a distorted tetrahedral fashion and forces ligand 1 to adopt two different conformations. Both phenomena are unique and cause an overall three-dimensional structure that has another confined, chiral, and hydrophilic central cavity.

Nanofibers from functionalized para-phenylene molecules

Tens to hundreds of micrometers long organic nanofibers have been generated from methoxy functionalized quaterphenylene molecules. The mutual alignment of the fibers is similar to that of previously reported nanofibers from para-hexaphenylene, and they emit intense, blue light centered at 400 nm with well resolved higher order vibronic peaks. The morphology is slightly different from that of para-hexaphenylene nanofibers, reflecting the different molecular structure. This study demonstrates that it is possible to generate organic nanofibers from artificially functionalized molecules and thus opens up the route to dedicated applications in new microdevices.

Synthesis, Resolution, and Absolute Configuration of Difunctionalized Tröger's Base Derivatives

Two racemic derivatives of Trögers base, the 2,8-diboronic acid ester 6 and the 3,9-dibromo-substituted derivative 5, were synthesized and successfully resolved by HPLC on a chiral stationary Whelk-01 phase on a semipreparative scale, thereby giving rise to both enantiomers in a pure form. These functionalized C(2)-symmetric building blocks are valuable precursors for a variety of further applications. Their absolute configurations were determined by comparison of their quantum chemically calculated CD and UV/Vis spectra with the experimental ones and were independently confirmed by X-ray diffraction 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.

Synthesis of 5-Substituted 2,2′-Bipyridines from Substituted 2-Chloropyridines by a Modified Negishi Cross-Coupling Reaction

A new and practical approach to a number of differently 5-substituted 2,2′-bipyridines starting from substituted 2-chloropyridines has been found through the application of modified Negishi cross-coupling conditions. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

New Carbaalanes − (AlMe)8(CCH2Me)5(C≡C−Me) and the THF Adduct (AlMe)8(CCH2Me)5H·2THF

The hydroalumination of Me2Al−C≡C−Me with a large excess of Me2AlH afforded the arachno-carbaalane (AlMe)8(CCH2Me)5H (4) by the release of AlMe3. 4 is almost insoluble in noncoordinating solvents and could not be purified by recrystallization. On an attempt to recrystallize 4 from a THF solution, the adduct (AlMe)8(CCH2Me)5H·2THF (5) was isolated as the first stable ether adduct of a carbaalane. Crystal structure determination revealed a cube of eight aluminium atoms, five faces of which are bridged by C−CH2Me groups. The sixth face is µ2-bridged by a hydrogen atom, and two opposite aluminium atoms of this face are coordinated by one THF ligand each. When the excess of dimethylaluminium hydride was reduced and the starting compounds were employed in a 1:2.1 molar ratio, an incomplete hydroalumination reaction led to the formation of the carbaalane (AlMe)8(CCH2Me)5(µ-C≡C−Me) (6), in which the bridging hydrogen atom of 4 is replaced by an alkynido group. 27Al NMR spectroscopic data of all the characterized carbaalanes are reported and supplemented by 27Al NMR chemical shift calculations.