Final Activity Report Summary - NANOMATCH (Supramolecular nanostructured organic/inorganic hybrid systems) The NANOMATCH project provided training excellence for researchers at the early stage of their careers in the field of opto-electronics, which plays a central role in the development of new communication and data processing technologies. While the project focused on basic research, potential applications of new findings were also explored. The interdisciplinary collaboration of ten academic and two industrial groups provided high-level training in a leading-edge research environment. The project aimed at the development of tailored photo- and electro-responsive organic/ inorganic hybrid systems by combining the advantages of organic and inorganic materials. Widespread application of cost-effective polymeric materials is mainly restricted by their limited chemical stability and lack of control of (inter-)molecular order. In the NANOMATCH approach, these limitations are overcome by hierarchical organisation of matter at different scales, i.e. by assembling nano-sized building blocks in a controlled way so that their optical and electronic properties can be advantageously matched to the macroscopic world. 1. Control on the molecular level was attained by the 'oligomer approach', by tailoring organic molecules and metal complexes for distinct applications such as colour-tuning, high photoluminescence (PL) and non-linear optics (NLO) efficiencies, as well as energy (ET) and charge (CT) transport properties. Specific functionalisation yielded probe molecules for the investigation of the effect of sterical and electrostatic constraints on inter- and intramolecular interactions. The synthetic efforts were guided by molecular design on a quantum-chemical basis. 2. Control at the nanoscale was achieved by the concept of supramolecular host-guest compounds, where active molecules are encapsulated in (in-)organic hosts, to obtain chemical stability, enhanced lasing-, PL-, NLO-, ET- and CT-efficiencies, as well as energy funnelling. The materials' functionality depends crucially on molecular order and dynamics of the guest molecules in the cavities of the host systems. Hence, we selected two complementary systems, an inert organic host and a strongly interacting inorganic host for in-depth experimental and computational studies which elucidated the impact of guest-guest and host-guest interactions on PL, ET and CT properties. 3. Control at the microscale was obtained by matching the nanostructured microscopic objects to the 'outside world', through self-assembly, deposition on patterned surfaces, and homogeneous dispersion in polymers. The stopcock principle, which connects HGCs to the outside world, was explored for different hosts and realising different head & tail units to mediate charge or exciton intrusion/extraction, supported by spectroscopic and computational studies. Highly aligned dye-filled color-tunable host crystals were realised in different dimensionalities, providing free standing 1D arrays, polymer-embedded micro-/nano-fibers, densely packed 2D layers, e.g. on (polymer-coated) transparent conductive oxides, and 3D arrangements. Holographic optical tweezers were used to manipulate 3D patterns in real-time and to deposit them on substrates. First prototypes of (white) light emitting diodes, new types of NIR emitters for telecommunication lasers and luminescent solar concentrators for solar energy harvesting were fabricated in this way. Several further applications, such as markers in bioassays, nanosensors or small scale optical devices are in sight NANOMATCH has provided an inventory of powerful tools for controlling the micro- and macroscopic arrangement of molecular building blocks, thus opening fascinating new possibilities in device technology, but also deepening the understanding of elementary processes such as energy- and charge-transfer in 3-dimensional molecular arrangements and at organic/inorganic interfaces.
