ABSTRACT
The self-assembly of bis-tridentate ligands leads to the spontaneous formation of [2 × 2] grid-like metal complexes. However, the synthesis of such ligands is rather cumbersome. In the work, we demonstrate a straightforward synthesis route to prepare bis-tridentate 4,6-bis((1H-1,2,3-triazol-4-yl)-pyridin-2-yl)-2-phenylpyrimidine ligands through double CuAAC click chemistry with 4,6-bis(6-ethynylpyridin-2-yl)-2-phenylpyrimidine as well as their self-assembly into [2 × 2] grid-like metal complexes. In addition, four macromolecular ligands were synthesized starting from azido-end-functionalized poly(2-ethyl-2-oxazoline) (PEtOx) or poly(ethylene glycol) (PEG). These macromolecular ligands were used in the construction of star-shaped supramolecular polymers through complexation with transition metal ions (e.g., Fe2+ or Zn2+). The successful fabrication of complexes and star-shaped polymers was confirmed by UV-vis titration measurements and MALDI-TOF mass spectrometry. However, the chemical structure of the polymer was found to have a strong influence on the [2 × 2] grid formation, which was successful with the PEG-ligands but not with the PEtOx-ligands, while the molecular weight of the PEG did not interfere with grid formation.
ABSTRACT
The greater chemical tunability of non-fullerene acceptors enables fine-tuning of the donor-acceptor energy level offsets, a promising strategy towards increasing the open-circuit voltage in organic solar cells. Unfortunately, this approach could open an additional recombination channel for the charge-transfer (CT) state via a lower-lying donor or acceptor triplet level. In this work we investigate such electron and hole back-transfer mechanisms in fullerene-free solar cells incorporating the novel molecular acceptor 2,4-diCN-Ph-DTTzTz. The transition to the low-driving force regime is studied by comparing blends with well-established donor polymers P3HT and MDMO-PPV, which allows for variation of the energetic offsets at the donor-acceptor interface. Combining various optical spectroscopic techniques, the CT process and subsequent triplet formation are systematically investigated. Although both back-transfer mechanisms are found to be energetically feasible in both blends, markedly different triplet-mediated recombination processes are observed for the two systems. The kinetic suppression of electron back-transfer in the blend with P3HT suggests that energy losses due to triplet formation on the polymer can be avoided, regardless of favorable energetic alignment.
