METALLACROWNS · based innovative materials and supramolecular devices

Metallacrowns-based innovative materials and supramolecular devices

The Marie Curie IRSES project “METALLACROWNS - Metallacrowns-based innovative materials and supramolecular devices” has been funded within the 7th Framework Programme of the EU, and took place from November 1st 2013 to October 31st 2017. As a Marie Curie IRSES, this project supported the mobility of researchers from EU to Ukraine and United States of America, and from Ukraine to European countries. Five EU institutions participated to this project: the Universitiy of Parma (Italy), the University of Wroclaw and the Adam Mickiewicz University in Poznan (Poland), the University of Paris-SUD and the CNRS Orleans (France). The Taras Shevchenko National University of Kiev (Ukraine) and the University of Michigan (USA) participated as non-EU countries: there two institutions have actually be the destination institutions of the mobility of the researchers from the EU. Along the four years of the project, the mobility scheme involved 32 researchers, among which 15 were early stage scientists (graduate students). Possibly more importantly, out of the 32 researchers involved in this mobility scheme 18 were women, this to demonstrate the extraordinary gender balance put in action by this consortium. Overall, the secondments carried out in this project amounted to over 93 person/months, with an average duration of each secondment of ca. 3 months. The scientific ground of this IRSES project has been the study of Metallacrowns (MC), which are a class of metal-based supramolecules, inorganic analogues of organic crown ethers. MC are characterized by several structural features that make them compounds with extraordinary properties. As self-assembled supramolecules they can be prepared by reacting organic ligands with metal ions to obtain the desired molecular frameworks in one single reaction step. Also, their self-assembly is guided by the geometry of the ligands and the coordination preferences of the metals, with the consequence that the formation of desired assemblies is highly predictable and they can be obtained in high yields. Perhaps most importantly, metallacrowns confine a large number of metal ions within a small single molecular framework. The principal consequence is that the metal ions can interact with each other and at the same time they are isolated from the environment. By virtue of all these features, metallacrowns exhibit peculiar physico-chemical properties: the extraordinary luminescence brightness or the single-molecule magnetic behavior of MC containing lanthanide ions are just examples of the functions of these supramolecules that have been investigated in this IRSES project. The collaborative research carried out in this project related with four major subtopics: 1) Metallacrowns as Single Molecule Magnets (SMMs); 2) Luminescent Metallacrowns for biological imaging; 3) Interaction of Metallacrowns with bioligands including DNA; 4) Three-dimensional porous Metallacrown assemblies. When considered as a whole, these subtopics cover a broad range of potentially exploitable application of metallacrowns. The experimental activities aimed at elucidating all structural and functional aspects of metallacrowns related with these four subtopics do require multiple competences that one single research group cannot deploy. For these reasons the consortium put together seven research groups: all seven groups are recognized leaders in the field of study of Metallacrowns, and could deploy competences that span from the synthesis of supramolecular complexes, to the study of their stability and assembly in solution, to the elucidation of their spectroscopic and magnetic properties and their reactivity. Important achievements and advancements of knowledge were obtained throughout all subtopics, which have been reported in 12 papers published on international scientific journals, and three Ph.D. dissertations. Possibly, the major advancements were obtained in the field of the luminescent metallacrowns for bioimaging of tissues and cells, as demonstrated by the release of three patents. The results obtained in the development of porous assemblies of Metallacrowns were also interesting, as demonstrated by the isolation of the first permanently porous metallacrown assembly capable to absorb gas molecules. The consortium has elucidated important aspects related with Metallacrowns as single-molecule magnets, in the perspective of the use of these compounds in data storage at the molecular level (quantum computers) and in spintronics devices. Finally, the demonstration that Metallacrowns interact with the telomeric domains of DNA have projected the research on metallacrowns deeply into the use of these complexes for the design of probes for the detection of specific biomolecules and for the imaging of specific cell compartments. Several Metallacrown systems have been protected by patent applications, although they are just examples of the previewed exploitable foreground developed in this project. Taking an overview to the scientific impact of the published research and of patented systems, it is beyond doubts that Metallacrowns will offer in the near future multiple opportunities to exploit probes, material and more in general devices with interest in medical diagnosis, theranostics, bio-and nanotechnology, quantum devices and information technology. Possibly more important, this project has consistently boosted the research on Metallacrowns also beyond the borders of this consortium as demonstrated by the ever growing number of scientific papers related to these compounds released in the past few years. Finally, there are important cultural aspects that have been positively impacted by this project. The first is undoubtedly the great opportunity that early stage researchers from seven EU institution, plus two from associated or partner countries, had to travel and be hosted at world leader laboratories to be trained on different skills and to carry out collaborative research. However, these secondments had an extraordinary cultural value: all researchers had the possibility to immerse themselves into social and cultural environments sometimes very different from those of their home countries. Further information, including a full list of deliverables and public reports of the secondments, can be found at the project website: https://sites.google.com/site/metallacrowns/. For any information, please contact the Primary Coordinator of the project: Dr. Matteo Tegoni (Department of Chemistry, Life Sciences, and Environmental Sustainability, University of Parma, Parma, Italy; matteo.tegoni@unipr.it).

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