Periodic Reporting for period 1 - Hy-solFullGraph (New hybrid-nanocarbon allotropes based on soluble fullerene derivatives in combination with carbon nanotubes and graphene. Application in organic solar cells and biomaterials.)
Période du rapport: 2017-05-01 au 2019-04-30
The aim of Hy-solFullGraph was to develop synthetic methodologies to yield new functional hybrid carbon allotropes with tuned solubility and to demonstrate their versatility for various technological applications.
The overall objectives were:
1-Tailoring the solubility of fullerenes and graphene by functionalisation with substituents of different natures (hydrophobic, hydrophilic, and polyfluorinated)
2-Selective functionalisation of fullerenes with appropiate reactive groups so that they can be used as nano-building-blocks for the assembly of hybrid SCAs nanostructures
3-Characterisation in terms of structure and functionality
Objectives 4 and 5 were related to their application, howbeit solubility problems together with the lack of activity caused a redirection of the project.
We have explored the selective functionalisation of different SCAs including fullerene, carbon nanotubes (CNTs), carbon nano-onions (CNOs) and graphene towards the synthesis of novel molecular hybrid architectures. New soluble fullerene building blocks ranging from superhydrophobic to hydrophilic have been synthesised and used as solubilising vectors to induce their solubility behaviour to other materials and to improve the processability. The solubility of nanocarbons is of paramount importance for their practical application, therefore this project has tackled an important issue to boost their use.
Hybrid-SCAs are currently a challenging area of research still at its infancy. Many interesting properties are envisioned for the hybrid combination of allotropes. For this porpouse, fullerenes with tailored solubility have been covalently attached to endohedral fullerene Sc3N@ C80 to induce a better solubility; the electronic interactions between the hybrid-SCAs are being studied. This is the first example of a dumbbell molecule combining and empty C60 fullerene with a cluster metallic one. Furthermore, other interesting Hybrids like graphene-C60 and CNT-C60 have been investigated.
This project has given important insights into functionalised fullerene properties helping to guide the design of new hybrid- materials with desirable properties like tunable solubility, which are in high demand for technological applications. Also this project shed light on the reductive functionalisation of multilayered fullerenes which is of great interest for the basic understanding of the role of defects and curvature on their reactivity.
The overall objectives were:
1-Tailoring the solubility of fullerenes and graphene by functionalisation with substituents of different natures (hydrophobic, hydrophilic, and polyfluorinated)
2-Selective functionalisation of fullerenes with appropiate reactive groups so that they can be used as nano-building-blocks for the assembly of hybrid SCAs nanostructures
3-Characterisation in terms of structure and functionality
Objectives 4 and 5 were related to their application, howbeit solubility problems together with the lack of activity caused a redirection of the project.
We have explored the selective functionalisation of different SCAs including fullerene, carbon nanotubes (CNTs), carbon nano-onions (CNOs) and graphene towards the synthesis of novel molecular hybrid architectures. New soluble fullerene building blocks ranging from superhydrophobic to hydrophilic have been synthesised and used as solubilising vectors to induce their solubility behaviour to other materials and to improve the processability. The solubility of nanocarbons is of paramount importance for their practical application, therefore this project has tackled an important issue to boost their use.
Hybrid-SCAs are currently a challenging area of research still at its infancy. Many interesting properties are envisioned for the hybrid combination of allotropes. For this porpouse, fullerenes with tailored solubility have been covalently attached to endohedral fullerene Sc3N@ C80 to induce a better solubility; the electronic interactions between the hybrid-SCAs are being studied. This is the first example of a dumbbell molecule combining and empty C60 fullerene with a cluster metallic one. Furthermore, other interesting Hybrids like graphene-C60 and CNT-C60 have been investigated.
This project has given important insights into functionalised fullerene properties helping to guide the design of new hybrid- materials with desirable properties like tunable solubility, which are in high demand for technological applications. Also this project shed light on the reductive functionalisation of multilayered fullerenes which is of great interest for the basic understanding of the role of defects and curvature on their reactivity.
Within the WP1 (Synthesis of selectively protected fullerenes with tailored solubility), a synthetic methodology to protect fullerenes based on the formation of an isoxazolino derivative that can be deprotected afterwards with mild photolytic conditions has been employed. The remaining positions were functionalised with 11 grous of different nature in order to demostrate the possibility to tune fullerene´s solubility from superhydrophobic to hydrophilic. The behaviour have been evaluated in solution (octanol/water partition coefficient) and on surface (contact angle meassurements). Moreover, the supramolecular self assembly has been adressed trough DSC, DLS and Cryo-TEM.
Along WP2 (Synthesise fullerene building blocks) the deprotection of the remaining position was achieved. This postion was subsequently functionalised with different anchoring groups as azides or alkynes for their use in click chemistry, amines as precursors for diazotation, iodine and carboxylic acids yielding fullerene building blocks with one reactive position. These building blocks are interesting candidates to use them in a lego-like approach in combination with other materials.
WP3 was dedicated to the synthesis of hybrid SCAs nanostructures. Different hybrids systems have been attempetd like graphene-C60, CNT-C60, C60-carbon nano-onios (CNOs) and C60-endohedral fullerene. This last hybrid have been reported as the first example of this type displaying very promising properties. The functionalisation with an appropiate group with complementary reactivity to that of the soluble fullerene has also been carried out for CNT, graphene, and CNO counterparts. An exhaustive characterisation with Raman, FTIR, TGA-GC-MS has been performed.
2 new WP were implemented since the initially planned applications failed. Instead, functionalisation of CNOs and synthesis of perylenebisimide cyclophanes as host system were investigated. The interesting outcomes resulting from this new part of the project will be published with the acknowledgment to the European Union’s Horizon 2020 programme under MSC grant agreement No. 747734.
Dr. Pérez-Ojeda ´s main results have been published in gold open acces and were highlited as hot paper with a cover and a frontiespiece:
-Chem.Commun. 2017, 53, 7886
-Chem.Eur.J. 2018, 24, 53, 14088
The researcher has disseminated the results at international conferences with 14 contributions. Moreover, she received the best poster award at 32th International Winterschool on Electronic Properties of Novel Materials, 2018, Kirchberg, Austria. Furthermore Dr. Pérez-Ojeda had the opportunity to attend the Marie Curie Alumni Annual Conference (MCAA) where she could learn about open access, European policies, project management and other translational skills
Along WP2 (Synthesise fullerene building blocks) the deprotection of the remaining position was achieved. This postion was subsequently functionalised with different anchoring groups as azides or alkynes for their use in click chemistry, amines as precursors for diazotation, iodine and carboxylic acids yielding fullerene building blocks with one reactive position. These building blocks are interesting candidates to use them in a lego-like approach in combination with other materials.
WP3 was dedicated to the synthesis of hybrid SCAs nanostructures. Different hybrids systems have been attempetd like graphene-C60, CNT-C60, C60-carbon nano-onios (CNOs) and C60-endohedral fullerene. This last hybrid have been reported as the first example of this type displaying very promising properties. The functionalisation with an appropiate group with complementary reactivity to that of the soluble fullerene has also been carried out for CNT, graphene, and CNO counterparts. An exhaustive characterisation with Raman, FTIR, TGA-GC-MS has been performed.
2 new WP were implemented since the initially planned applications failed. Instead, functionalisation of CNOs and synthesis of perylenebisimide cyclophanes as host system were investigated. The interesting outcomes resulting from this new part of the project will be published with the acknowledgment to the European Union’s Horizon 2020 programme under MSC grant agreement No. 747734.
Dr. Pérez-Ojeda ´s main results have been published in gold open acces and were highlited as hot paper with a cover and a frontiespiece:
-Chem.Commun. 2017, 53, 7886
-Chem.Eur.J. 2018, 24, 53, 14088
The researcher has disseminated the results at international conferences with 14 contributions. Moreover, she received the best poster award at 32th International Winterschool on Electronic Properties of Novel Materials, 2018, Kirchberg, Austria. Furthermore Dr. Pérez-Ojeda had the opportunity to attend the Marie Curie Alumni Annual Conference (MCAA) where she could learn about open access, European policies, project management and other translational skills
Hy-solFullGraph has redressed one of the main problems that hamper the application of carbon materials: the lack of solubility. The developed methodology is an usefull tool for the preparation of à la carte building blocks with the desired hydrophobic/hydrophilic behaviour that can be covalently bind to other Synthetic Carbon Allotropes (SCAs). New Hybrid combinations of SCAs have been isolated and characterised for the very first time demostrating the great potencial of these new materials. Furthermore, functional molecules with possible application in the field of catalysis, sensoring and selective encapsulation have been prepared and their properties are being currently evaluated. In overall, this project might help to design new functional materials with tuned properties as required by the applications. Also, it has provided some important insights into the relationship between structure and properties.
Regarding the impact on the career prospects of the researcher, the MSC Fellowship has provided:
-broad scientific training in state-of-the-art techniques
-independent management from the definition of the project, experimental development, data analysis and result communication
-publication in high impact journals and dissemination of results at international conferences
-transfer the gained knowledge by providing teaching support to students
-establish a strong and lasting collaboration network
All these have significantly enhanced her skills and have reinforced her capacities to attract funding in order to consolidate her career. This MSC action, has allowed to establish herself as a fully independent researcher in the field of Materials Science. She is currently applying as PI for a coordinate project from the German research foundation (DFG). Furthermore, she has been recently granted with a fellowship from FAU and the Bavarian government to continue her research and the Emerging Talent´s initiative from FAU.
The project had also impact in society, Dr.Pérez-Ojeda have been involved in public engagement talks to guide young students trough the applications for funding. Also, she has organized an international conference promoting women in Science (Women in Science, 1st Erlangen symposium, 2018)
Regarding the impact on the career prospects of the researcher, the MSC Fellowship has provided:
-broad scientific training in state-of-the-art techniques
-independent management from the definition of the project, experimental development, data analysis and result communication
-publication in high impact journals and dissemination of results at international conferences
-transfer the gained knowledge by providing teaching support to students
-establish a strong and lasting collaboration network
All these have significantly enhanced her skills and have reinforced her capacities to attract funding in order to consolidate her career. This MSC action, has allowed to establish herself as a fully independent researcher in the field of Materials Science. She is currently applying as PI for a coordinate project from the German research foundation (DFG). Furthermore, she has been recently granted with a fellowship from FAU and the Bavarian government to continue her research and the Emerging Talent´s initiative from FAU.
The project had also impact in society, Dr.Pérez-Ojeda have been involved in public engagement talks to guide young students trough the applications for funding. Also, she has organized an international conference promoting women in Science (Women in Science, 1st Erlangen symposium, 2018)