Arylic versus Alkylic-Hydrophobic Linkers Determine the Supramolecular Structure and Optoelectronic Properties of Tripodal Amphiphilic Push-Pull Thiazoles.

The supramolecular structures and their constituents essentially determine the optoelectronic properties of thin films. The introduction of amphiphilicity to the constituents and interface assembly is one established technique to control supramolecular structures and resulting material properties. To yield amphiphilicity, rather hydrophobic chromophores are linked to hydrophilic head groups via flexible alkyl chains. In the present work, we investigate whether replacement of the alkyl linkers by a phenylene linker, that is, replacing an electrically isolating moiety with a potentially semiconducting one, increases the conductivity through the resulting layers. After investigating the influence of the linker on molecular properties of the 2-(4- N, N-dimethylaminophenyl)-4-hydroxy-5-nitrophenyl-1,3 thiazoles exemplarily used in this work, we produce supramolecular structures by means of the Langmuir-Blodgett (LB) technique. Atomic force microscopy (AFM) and UV-vis absorption spectroscopy reveal that thin films made from the more rigid thiazole bearing the arylic linker feature a more homogeneous and stable supramolecular structure as compared to those made from the thiazole dye containing the flexible alkylic linker. Finally, conductive AFM (cAFM) results disclose that the LB films made from the thiazole bearing the π-conjugated arylic linker are less conductive than their counterparts based on the alkylic linkers. In the latter layers, the alkylic linkers provide sufficient motional degrees of freedom to allow for supramolecular rearrangement upon electrical operation during cAFM measurements, hence yielding supramolecular structures featuring increased conductivity with successive cAFM measurements. This work highlights the importance of supramolecular structures for optoelectronic properties by presenting a case where supramolecular effects excel the property changes introduced by molecular modifications.

Enhancing the supramolecular stability of monolayers by combining dipolar with amphiphilic motifs: a case of amphiphilic push-pull-thiazole.

Equipping a thiazole dye with push and pull moieties adds dipolar intermolecular interactions and two hydrophilic anchors to a centrally anchored π-stacking and otherwise mono-amphiphilic dye. We show that, despite the resulting irregular shape of the tripodal amphiphile, the enhanced intermolecular interactions and amphiphilicity yield smooth and stable thin films. Furthermore, we present a first approach for deriving supramolecular binding energies from the Langmuir-Blodgett hysteresis data.

Introducing double polar heads to highly fluorescent Thiazoles: Influence on supramolecular structures and photonic properties.

HYPOTHESIS: Supramolecular structures determine properties of optoelectronically active materials and can be tailored via the Langmuir-Blodgett (LB) technique. Interactions between dyes can cause high crystallinities of Langmuir monolayers, thus rendering retaining their integrity during the LB-deposition challenging. However, increasing degrees of freedom exclusively at the polar anchoring moieties of dyes might improve processability without perturbing the dye's optoelectronic properties nor the function-determining crystallinity of the layer. EXPERIMENTS: (Amphiphilic) thiazole dyes without, with a mono-polar, and with a double-polar anchor were synthesized, whereas the two constituting polar moieties of the latter derivate are separated by a flexible alkyl chain. The supramolecular structures and crystallinities of Langmuir and LB monolayers were characterized by means of LB isotherms, atomic force microscopy and polarization-resolved fluorescence spectroscopy. FINDINGS: As compared to the mono-polar reference the introduction of a flexible double-polar head did not deteriorate UV-vis absorption, emission or electrochemical properties of the thiazole but significantly extended the range of constant compressibility modulus, thus indicating improved processability of the Langmuir monolayers. Indeed, AFM studies revealed that the integrity of the monolayers could be retained during LB-deposition. Additionally, also the underlying supramolecular structure of the chromophore moieties is largely identical to those obtained from the mono-polar reference thiazoles.