Potential host systems based on a rigid 1,8-diethynylanthracendiyl backbone were synthesised by treatment of 1,8-diethynylanthracene with the Group 13 trialkyls AlMe(3), GaMe(3), InMe(3), AlEt(3) and GaEt(3). The resulting products were characterised by IR and multinuclear NMR spectroscopy, elemental analyses and determination of their crystal structures by X-ray diffraction. The compounds are dimeric in the solid state and comprise two M(2)C(2) heterocycles. Depending on the steric demand of the alkyl substituents at the metal atom, different types of binding modes were observed, which can be classified to lie between the ideals of side-on coordination with almost linear primary M-C≡C units and the 3c-2e coordination with symmetrically bridging alkynyl units in M-C-M bonds. As a solution in THF the dimers are broken into monomers and some are found to undergo ligand scrambling reactions.

A series of bis- and tris[(trimethylsilyl)ethynyl]anthracenes (1,5-, 1,8-, 9,10- and 1,8,10-) has been synthesised by multistep (cross coupling) reactions and the behaviour of the SiMe3-functionalised alkynylanthracene derivatives towards UV irradiation was qualitatively studied by NMR spectroscopy. In the case of 9,10-bis[(trimethylsilyl)ethynyl]anthracene we observed a photodimerisation upon UV irradiation; the third example was reported for a symmetrically 9,10-difunctionalised anthracene derivative, besides those with small fluorine- and methyl-substituents. The anthracene dimerisation is completely thermally reversible and the temperature dependence of the cycloelimination reaction was studied by (1)H VT-NMR experiments. The (deprotected) 1,5- and 1,8-diethynylanthracenes were converted with (dimethylamino)trimethylstannane to obtain the corresponding SnMe3-functionalised alkynes, potentially useful as highly conjugated building blocks in Stille cross coupling reactions. The new anthracene compounds were completely characterised by multinuclear NMR spectroscopy, (high resolution) mass spectrometry and - in most cases - by X-ray diffraction experiments.

The formation of host-guest (H-G) complexes between 1,8-bis[(diethylgallanyl)ethynyl]anthracene (H) and the N-heterocycles pyridine and pyrimidine (G) was studied in solution using a combination of NMR titration and diffusion NMR experiments. For the latter, diffusion coefficients of potential host-guest structures in solution were compared with those of tailor-made reference compounds of similar shape (synthesized and characterized by NMR, HRMS, and in part XRD). Highly dynamic behavior was observed in both cases, but with different host-guest species and equilibria. With increasing concentrations of the pyridine guest, the equilibrium H2⇄H2κ(1)-G1⇄HG2 is observed (in the second step a host dimer coordinates one guest molecule); for pyrimidine the equilibrium H2→H1κ(2)-G1⇄HG2 is observed (the formation of a 1:1 aggregate is the second step).

A series of 1,8-dichloroanthracene precursor molecules with substituents in C-10 position of different steric demand (cyclohexyl, tert-butyl, methyl, isopropyl, n-butyl, phenyl, benzyl, trimethylsilylethinyl) were synthesised and subjected to electrocyclic cycloadditions with chlorobenzyne generated from 3-chloroanthranilic acid. The aim was to steer the regioselectivity of the addition reaction by the steric repulsion between this C-10 substituent and the chlorine substituent at the benzyne intermediate. With H as C-10 substituent the reaction leads to 23 % syn and 77 % anti form. With the small methyl group a syn/anti ratio of 37:63 was achieved. Contrary to our expectations the large C-10 substituent tert-butyl