Proiect PN-III-P1-1.1-PD-2016-0646:
Project timespan
Project team
Abstract
Project objectives
Budget
Results
Title: Molecular dynamic systems based on hybrid oligothiophenes as multi-stage redox-controlled actuators
Contract: 24/02.05.2018
Project timespan
2018 -- 2020
2018 -- 2020
Abstract
The main goal of this project is to develop a new class of molecular actuators based on an original concept involving the use of constructive and/or destructive coulombic interactions created by modifying the redox state of two redox active units covalently organized in a face-to-face arrangement in a macrocycle. The oxidation of AA macrocyclic system to the stable dication state (A+A+) produces coulombic repulsion between the positive charges leading to a deformation of the cyclophane-type system by pushing away the two positively charged moieties. A more advanced version of this basic concept allows the envision more complex multi-stage systems. In this case, instead of a unique redox active unit, two different systems (A and B) are associated, which can be oxidized to stable cation-radical and stable dication stages. In the neutral form (AB), the two constituents exhibit different electronic densities (one is electron rich and the other is electron pour) and the A and B units are close one to the other. The oxidation of A and B to their cation-radical forms determine the presence of two positively charges platforms in the macrocycle [A (+), B (+)], and this one will adopt a new conformation with A and B units pushed away. The further oxidation of A and B to their dicationic forms [A (++), B (++)] will determine more dramatical conformational changes in the macrocycle, and A and B units will be pushed at an even higher distance. The reversed redox processes will bring back the system to the initial conformations and so these molecular actuators can be easily electrochemically controlled. The two proposed redox active entities are based on TTF (tetrathiafulvallene) and tetrakisthiophene [displaying no, one or two EDOT (ethylenedioxythiophene) units] moieties which exhibit well known electrochemical behaviors. Intermediate stages are possible and if these ones are also isolated the multistage work of the proposed machines are even more complex.
The main goal of this project is to develop a new class of molecular actuators based on an original concept involving the use of constructive and/or destructive coulombic interactions created by modifying the redox state of two redox active units covalently organized in a face-to-face arrangement in a macrocycle. The oxidation of AA macrocyclic system to the stable dication state (A+A+) produces coulombic repulsion between the positive charges leading to a deformation of the cyclophane-type system by pushing away the two positively charged moieties. A more advanced version of this basic concept allows the envision more complex multi-stage systems. In this case, instead of a unique redox active unit, two different systems (A and B) are associated, which can be oxidized to stable cation-radical and stable dication stages. In the neutral form (AB), the two constituents exhibit different electronic densities (one is electron rich and the other is electron pour) and the A and B units are close one to the other. The oxidation of A and B to their cation-radical forms determine the presence of two positively charges platforms in the macrocycle [A (+), B (+)], and this one will adopt a new conformation with A and B units pushed away. The further oxidation of A and B to their dicationic forms [A (++), B (++)] will determine more dramatical conformational changes in the macrocycle, and A and B units will be pushed at an even higher distance. The reversed redox processes will bring back the system to the initial conformations and so these molecular actuators can be easily electrochemically controlled. The two proposed redox active entities are based on TTF (tetrathiafulvallene) and tetrakisthiophene [displaying no, one or two EDOT (ethylenedioxythiophene) units] moieties which exhibit well known electrochemical behaviors. Intermediate stages are possible and if these ones are also isolated the multistage work of the proposed machines are even more complex.
Main objectives
1.Synthesis and characterization of quaterthiophenes macrocycles containing maximum one EDOT unit.
1.1. Synthesis and characterization of intermediates.
1.2. Synthesis and characterization of macrocycles.
1.3. Investigations on the role of actuators of synthesized compounds.
2. Synthesis and characterization of quatertiophenes macrocycles containing two EDOT units.
2.1. Synthesis and characterization of intermediates.
2.2. Macrocycles synthesis and characterization.
2.3. Investigations on the role of actuator of synthesized compounds.
3. TTF-ammonium salt macrocycles. Models of molecular actuators.
3.1. Synthesis, characterization and function as molecular actuators of TTF-ammonium salts macrocycles.
1.Synthesis and characterization of quaterthiophenes macrocycles containing maximum one EDOT unit.
1.1. Synthesis and characterization of intermediates.
1.2. Synthesis and characterization of macrocycles.
1.3. Investigations on the role of actuators of synthesized compounds.
2. Synthesis and characterization of quatertiophenes macrocycles containing two EDOT units.
2.1. Synthesis and characterization of intermediates.
2.2. Macrocycles synthesis and characterization.
2.3. Investigations on the role of actuator of synthesized compounds.
3. TTF-ammonium salt macrocycles. Models of molecular actuators.
3.1. Synthesis, characterization and function as molecular actuators of TTF-ammonium salts macrocycles.
Budget
| Budget chapter (expenses) | 2018 (lei) | 2019 (lei) | 2020 (lei) | Total | |
|---|---|---|---|---|---|
| 1 | Salaries | 56.400 | 84.600 | 28.200 | 16.9200 |
| 2 | Inventory | 16.148 | 20.352 | 2.700 | 39.200 |
| 3 | Mobility | 0 | 7.800 | 2.000 | 9.800 |
| 4 | Overhead | 9.952 | 16.913 | 4.935 | 31.800 |
| 5 | Total | 82.500 | 129.665 | 37.835 | 250.000 |
Results
1.1. Synthesis and characterization of intermediates, precursors for the quatertthiophenes macrocycles containing maximum one EDOT unit. Reports
1.1. Synthesis and characterization of intermediates, precursors for the quatertthiophenes macrocycles containing maximum one EDOT unit. Reports
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The yearly scientific reports containing experimental details of unpublished compounds data can be provided for project evaluation purposes only. Dr. Monica-Irina Nan(nee Rednic) at mrednic (at) chem.ubbcluj.ro .