Hexaguanidino-Triptycenes and Triphenylenes: Electronic Coupling in Molecules Containing Three Redox-Active o-Diguanidinobenzene Units Connected either Directly or Interacting Through Homoconjugation.

Novel redox-active hexaguanidine molecules with multiple redox states were synthesized by connecting three o-diguanidinobenzene units. In 2,3,6,7,14,15-hexaguanidino-triptycenes, the three redox-active o-diguanidinobenzene units are connected through C-C bonds to the sp3 -hybridized bridgehead C atoms, and in 2,3,6,7,10,11-hexaguanidino-triphenylenes they are directly connected. The connectivity difference leads to different electronic coupling between the three redox-active o-diguanidinobenzene units, with homoconjugation being present in the triptycene, but not in the triphenylene compounds. Motivated by the appearance of an intense low-energy electronic transition, we especially analysed the effect of homoconjugation on the electronic structure and charge delocalization in the dicationic redox state of the triptycene derivatives. Then, several trinuclear high-spin cobalt (and copper) complexes were synthesized with the triphenylene and triptycene ligands, and the magnetic coupling and redox properties analysed. By choice of the coligands (hexafluoroacetylacetonate, trifluoroacetylacetonate and acetylacetonate), oxidation could be switched between metal- and ligand-centered redox events, leading to drastic changes in the magnetic or optical properties, especially as a consequence of homoconjugation in the triptycene derivatives.

Asymmetric optical multimode splitters by field-assisted ion exchange using patterned mask openings.

Asymmetric optical multimode splitters based on optical waveguides were fabricated in glass substrates using a field-assisted ion exchange process. Accompanying simulations, conducted to study the light propagation, revealed the possibility to realize asymmetric splitters based on waveguides with different width. In the exchange process, broad mask openings in the blocking layer are compared to those consisting of closely spaced parallel lines with various widths. The waveguide profiles of the resulting splitters were recorded and the optical losses and splitting ratios were determined for a wavelength of 850 nm. Additionally data transmission tests were conducted and showed the suitability of the splitters for a bandwidth of 28 GBit/s.

Use of Crown Ether Functions as Secondary Coordination Spheres for the Manipulation of Ligand-Metal Intramolecular Electron Transfer in Copper-Guanidine Complexes.

Intramolecular electron transfer (IET) between a redox-active organic ligand and a metal in a complex is of fundamental interest and used in a variety of applications. In this work it is demonstrated that secondary coordination sphere motifs can be applied to trigger a radical change in the electronic structure of copper complexes with a redox-active guanidine ligand through ligand-metal IET. Hence, crown ether functions attached to the ligand allow the manipulation of the degree of IET between the guanidine ligand and the copper atom through metal encapsulation.

Use of Crown Ether Functions as Secondary Coordination Spheres for the Manipulation of Ligand-Metal Intramolecular Electron Transfer in Copper-Guanidine Complexes.

Invited for the cover of this issue is the group of Hans-Jörg Himmel at Ruprecht-Karls-Universität Heidelberg. The image depicts the electron transfer process using copper complexes with redox-active guanidines. Read the full text of the article at 10.1002/chem.202003469.