Luminescent coordination-driven supramolecular assemblies based on pre-organized Cu(I) precursors stabilized by main-group element ligands – SUPRALUM

A combined experimental and computational approach will be performed that will unify the fundamental understanding and application of coordination and supramolecular chemistry, main-group elements chemistry, photophysics and material sciences. For the first time, the specific and complementary synthetic tools and characterisation skills available in both the German and the French group (such as the coordination-driven supramolecular chemistry adapted to flexible Cu(I) pre-assembled precursors as well as the innovative use of polytopic assembling main group (P, As, Sb, Bi) ligand complexes and of fully aliphatic and flexible polytopic linkers) will be combined in order to specifically introduce luminescence properties within the targeted polymetallic supramolecular scaffolds, conferring a significant level of novelties to this project. State-of-the-art photophysical investigations and calculations will be executed to highlight luminescence properties and rationalise electronic processes that are inherent in the synthesised new materials
By an intensive collaborative work, rapid and remarkable progress will be achieved.
In order to achieve the objectives of the project, we propose to establish a scientific program, which can be categorised into 3 major tasks:
1. Design and synthesis of pre-organised polymetallic Cu(I) precursors and their supramolecular assemblies as well as their spectroscopic and solid state structure characterisation.
2. Extended photophysical characterisation of the polymetallic Cu(I) supramolecular assemblies.
3. Quantum-chemical studies of the chemical bonding, ground-state and excited-state molecular structures, excited-state energy and radiative relaxation processes of the polymetallic Cu(I) supramolecular assemblies.

Innovative coordination-driven supramolecular synthetic routes already mastered by the consortium members will be adapted to new straightforward high-yield syntheses of polymetallic Cu(I) derivatives. An unprecedentedly thorough study of the structure-property relationships of such luminescent supramolecular compounds will be conducted, inducing a significant growth of the family of luminescent Cu(I) derivatives to establish an emerging and promising class of emissive molecular materials.
A thorough study of the structure-property relationships of such luminescent supramolecular compounds will be conducted and induce a significant growth of the family of the studied multifunctional luminescent Cu(I) ion derivatives. From the large library of new luminescent Cu(I) supramolecular complexes that will be obtained, the most promising derivatives (in terms of photophysical and multi-functional properties, easing synthesis, etc.) will be selected to be incorporated into various matrices and substrates leading to the preparation of suitable materials for technological applications.

On the basis of the encouraging first results obtained by both the German and French groups, substantial guarantees are provided that this project will generate new scientific knowledge and innovative classes of environmentally friendly, multifunctional luminescent materials that are highly relevant in the line of sustainable development. The specific and appealing photophysical properties potentially embedded in the Cu(I) derivatives allow to consider them as unique synthetic tools to introduce, in a general way, luminescence properties in coordination-driven supramolecular assemblies. Therefore, they offer very versatile entries to the design of innovative and efficient solid-state emissive materials, but also as new multifunctional luminescent sensors. That will lead to important findings in the area of basic research, but also deliver scientifically sound and technologically important results for further applications. The joint research efforts currently conducted both in Germany and in France will therefore be enhanced and cross-fertilized to promote this area of research, which is highly relevant to sustainable energy and materials research. Likewise, such an integrated bi-national, inter-institutional and interdisciplinary ANR-DFG joint research programme will also provide an all-round training of the participating research postgraduates, postdoctoral fellows and young research scientists. An intensive scientific exchange of doctoral students will be a priority to allow for efficient and rapid progress and to enhance the international skills of the students.

The present project will generate new classes of light-emitting original Cu(I) polymetallic supramolecular assemblies with tunable emission and absorption characteristics and energies that will lead to possible patent portfolio, but will also deliver scientifically sound and technologically important results. This SUPRALUM project will generate findings that will no doubt be of great benefit to not only the consortium members but also industries, contributing towards the advancement of cheap luminescent molecular materials for optoelectronic applications from large-scale lighting application and displays to multifunctional detectors. Results dissemination through publications in high impact international journals will be also a decisive target, as well as presentations in national and international conferences for all the members involved in this project, including the non-permanent PhD and post-doctoral students.

Given the deficit of inexpensive and luminescent materials from compounds containing abundant elements as for instance copper, this ANR-DFG SUPRALUM project targets the preparation and the study of the multifunctional luminescence properties of a large series of new discrete and polymeric polymetallic Cu(I) based supramolecular assemblies. These new inexpensive and stable derivatives will present unprecedented architectures that include enhanced solid-state luminescence properties, which will establish them as a very appealing source of new multifunctional molecular materials incorporating both lighting and sensor applications. A combined experimental and computational approach will be performed that will unify the fundamental understanding and application of coordination and supramolecular chemistry, main-group elements chemistry, photophysics and material sciences. Innovative coordination-driven supramolecular synthetic routes already mastered by the consortium members will be adapted to new straightforward high-yield syntheses of polymetallic Cu(I) derivatives. For the first time, the specific and complementary synthetic tools and characterisation skills available in both the German and the French group (such as the coordination-driven supramolecular chemistry adapted to flexible Cu(I) pre-assembled precursors as well as the innovative use of polytopic assembling main group (P, As, Sb, Bi) ligand complexes and of fully aliphatic and flexible polytopic linkers) will be combined in order to specifically introduce luminescence properties within the targeted polymetallic supramolecular scaffolds, conferring a significant level of novelties to this project. State-of-the-art photophysical investigations and calculations will be executed to highlight luminescence properties and rationalise electronic processes that are inherent in the synthesised new materials. It will thus be possible to execute an unprecedentedly thorough study of the structure-property relationships of such luminescent supramolecular compounds, inducing a significant growth of the family of luminescent Cu(I) derivatives to establish an emerging and promising class of emissive molecular materials. Very encouraging first results have been obtained by both the German and French groups that are the basis of their cooperation, providing substantial guarantees that this project will generate new scientific knowledge and innovative classes of environmentally friendly, multifunctional luminescent materials that are highly relevant in the line of sustainable development.