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Spontaneous phase separation of materials is a powerful strategy to generate highly defined 2D nanomorphologies with novel properties and functions. Exemplary are such morphologies in block copolymers or amphiphilic systems, whose formation can be well predicted based on parameters such as volume fraction and shape factor. In contrast, the formation of 2D nanomorphologies is currently unpredictable in materials perfectly defined at the molecular level, in which crystallinity plays a significant role. Here, we introduce a crystal lattice analysis to predict a priori the formation of 2D nanomorphologies from the crystalline units in phase-separated soft materials. We show that the formation of lamellar morphologies, their domain spacings, and thermal transition temperatures of such materials can be predicted using a straightforward crystal lattice analysis workflow. We envision this approach to facilitate the design and discovery of new materials with 2D nanomorphologies that are essential for next-generation electronic applications.

Efficient energy transport over long distances is essential for optoelectronic and light-harvesting devices. Although self-assembled nanofibers of organic molecules are shown to exhibit long exciton diffusion lengths, alignment of these nanofibers into films with large, organized domains with similar properties remains a challenge. Here, it is shown how the functionalization of C 3 -symmetric carbonyl-bridged triarylamine trisamide (CBT) with oligodimethylsiloxane (oDMS) side chains of discrete length leads to fully covered surfaces with aligned domains up to 125 × 70 µm 2 in which long-range exciton transport takes place. The nanoscale morphology within the domains consists of highly ordered nanofibers with discrete intercolumnar spacings within a soft amorphous oDMS matrix. The oDMS prevents bundling of the CBT fibers, reducing the number of defects within the CBT columns. As a result, the columns have a high degree of coherence, leading to exciton diffusion lengths of a few hundred nanometers with exciton diffusivities (≈0.05 cm 2 s -1 ) that are comparable to those of a crystalline tetracene. These findings represent the next step toward fully covered surfaces of highly aligned nanofibers through functionalization with oDMS., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The assembly of donor-acceptor molecules via charge transfer (CT) interactions gives rise to highly ordered nanomaterials with appealing electronic properties. Here, we present the synthesis and bulk co-assembly of pyrene (Pyr) and naphthalenediimide (NDI) functionalized oligodimethylsiloxanes (oDMS) of discrete length. We tune the donor-acceptor interactions by connecting the pyrene and NDI to the same oligomer, forming a heterotelechelic block molecule (NDI-oDMSPyr), and to two separate oligomers, giving Pyr and NDI homotelechelic block molecules (Pyr-oDMS and NDI-oDMS). Liquid crystalline materials are obtained for binary mixtures of Pyr-oDMS and NDI-oDMS, while crystallization of the CT dimers occurred for the heterotelechelic NDI-oDMS-Pyr block molecule. The synergy between crystallization and phase-segregation coupled with the discrete length of the oDMS units allows for perfect order and sharp interfaces between the insulating siloxane and CT layers composed of crystalline CT dimers. We were able to tune the lamellar domain spacing and donor-acceptor CT interactions by applying pressures up to 6 GPa on the material, making the system promising for soft-material nanotechnologies. These results demonstrate the importance of the molecular design to tune the CT interactions and stability of a CT material.

Materials based on the laminar ordering of self-assembled molecules have a unique potential for applications requiring efficient energy migration through densely packed chromophores. Here, employing molecular assemblies of coil-rod-coil block molecules for triplet-triplet annihilation upconversion (TTA-UC) based on triplet energy migration with linearly polarized emission is reported. By covalently attaching discrete-length oligodimethylsiloxane (oDMS) to 9,10-diphenylanthracene (DPA), highly ordered 2D crystalline DPA sheets separated by oDMS layers are obtained. Transparent films of this material doped with small amounts of triplet sensitizer Pt II octaethylporphyrin show air-stable TTA-UC under non-coherent excitation. Upon annealing, an increase in TTA-UC up to two orders of magnitude is observed originating from both an improved molecular ordering of DPA and an increased dispersion of the sensitizer. The molecular alignment in millimeter-sized domains leads to upconverted linearly polarized emission without alignment layers. By using a novel technique, upconversion imaging microscopy, the TTA-UC intensity is spatially resolved on a micrometer scale to visually demonstrate the importance of molecular dispersion of sensitizer molecules for efficient TTA-UC. The reported results are promising for anti-counterfeiting and 3D night-vision applications, but also exemplify the potential of discrete oligodimethylsiloxane functionalized chromophores for highly aligned and densely packed molecular materials., (© 2020 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The scope and accessibility of sequence-controlled multiblock copolymers is demonstrated by direct "in situ" polymerization of hydrophobic, hydrophilic and fluorinated monomers. Key to the success of this strategy is the ability to synthesize ABCDE, EDCBA and EDCBABCDE sequences with high monomer conversions (>98 %) through iterative monomer additions, yielding excellent block purity and low overall molar mass dispersities (Ð<1.16). Small-angle X-ray scattering showed that certain sequences can form well-ordered mesostructures. This synthetic approach constitutes a simple and versatile platform for expanding the availability of tailored polymeric materials from readily available monomers., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Crystallinity is seldomly utilized as part of the microphase segregation process in ultralow-molecular-weight block copolymers. Here, we show the preparation of two types of discrete, semicrystalline block co-oligomers, comprising an amorphous oligodimethylsiloxane block and a crystalline oligo-l-lactic acid or oligomethylene block. The self-assembly of these discrete materials results in lamellar structures with unforeseen uniformity in the domain spacing. A systematic introduction of dispersity reveals the extreme sensitivity of the microphase segregation process toward chain length dispersity in the crystalline block.