Proiect PN-II-RU-TE-2014-4-0727:
Project timespan
Project team
Abstract
Project objectives
Budget
Results
Title:
Project manager: Conf. Dr. Niculina D. Hădade ResearcherID: F-9489-2011
Team:
- Dr. Andreea Diac
- Lidia Pop
- Gabrian Levi Mihai
- Virlan (cas. Mate) Nadejda
Project timespan
2015 -- 2017
2015 -- 2017
Abstract
Development of 3D molecular organic cages with large internal cavities has emerged as an important research area of supramolecular chemistry mainly due to their usefulness as host molecules with enhanced guest binding properties, nanoporous materials with well-defined pores and large internal surface area as well as sensors. Among the most important challenges in the achievement of such molecules we can mention their laborious multi-step synthesis and the difficulty to preserve the integrity of the internal cavity in the solid state. Herein, we propose the design and synthesis of rigid and semi-flexible naphthalene diimide-based 3D cage molecules with trigonal prismatic, square prismatic and hexagonal prismatic geometries as proper candidates to obtain materials with improved gas absorption capacities as well as selective receptors for organic small molecules. Moreover, considering the electronic and spectroscopic properties of the naphthalene diimide units, the proposed structures meet the requirements of molecular sensors. One-pot or sequential dynamic synthesis using imine exchange and/or alkynes metathesis reversible reactions in a classical dynamic covalent chemistry (DCC) process will be used in order to achieve the target structures. In addition, taking advantage of the orthogonality between the imine formation and alkynes metathesis, an Orthogonal Dynamic Covalent Chemistry (ODCC) strategy shall also be used for the synthesis of the cage compounds.
Development of 3D molecular organic cages with large internal cavities has emerged as an important research area of supramolecular chemistry mainly due to their usefulness as host molecules with enhanced guest binding properties, nanoporous materials with well-defined pores and large internal surface area as well as sensors. Among the most important challenges in the achievement of such molecules we can mention their laborious multi-step synthesis and the difficulty to preserve the integrity of the internal cavity in the solid state. Herein, we propose the design and synthesis of rigid and semi-flexible naphthalene diimide-based 3D cage molecules with trigonal prismatic, square prismatic and hexagonal prismatic geometries as proper candidates to obtain materials with improved gas absorption capacities as well as selective receptors for organic small molecules. Moreover, considering the electronic and spectroscopic properties of the naphthalene diimide units, the proposed structures meet the requirements of molecular sensors. One-pot or sequential dynamic synthesis using imine exchange and/or alkynes metathesis reversible reactions in a classical dynamic covalent chemistry (DCC) process will be used in order to achieve the target structures. In addition, taking advantage of the orthogonality between the imine formation and alkynes metathesis, an Orthogonal Dynamic Covalent Chemistry (ODCC) strategy shall also be used for the synthesis of the cage compounds.
Budget
| Budget chapter (expenses) | 2015 (lei) | 2016 (lei) | 2017 (lei) | Total | |
|---|---|---|---|---|---|
| 1 | Salaries | 29.000 | 135.200 | 145.904 | 299.904 |
| 2 | Inventory | 5.869,57 | 68.759,65 | 88.727,64 | 163.356,86 |
| 3 | Mobility | 0 | 5.555,13 | 9.444,87 | 15.000 |
| 4 | Overhead | 10.130,43 | 31.427,22 | 30.181,49 | 71.739,14 |
| 5 | Total | 45.000 | 240.942 | 264.058 | 550.000 |
Results
- Synthesis and characterization of the 3D cages intermediate: ethinyl-, formyl- and amino-decorated corner units as well as ethynyl and amino-ended linkers.
- Synthesis and characterization of naphthalene diimide based macrocycles.
- Development of a new method for selective hydration of activated aromatic alkynes using a Mo(VI) catalyst.
- Synthesis and characterization of 3D cages with triazine and pyridine units.
- Investigation of the complexation properties of the obtained macrocycles and cages using neutral guests molecules.
- Investigation of photoelectronic and redox properties of the obtained macrocycles and cages.
Articles
- Naphthalenediimide - a unique motif in macrocyclic and interlocked supramolecular structures,
Andreea Diac, Mihaela Matache, Ion Grosu and Niculina D. Hădade Advanced Synthesis and Catalysis, 2017, DOI: 10.1002/adsc.201701362 - Three armed cryptand with triazine and pyridine units: synthesis, structure and complexation with polycyclic aromatic compounds,
Claudia Lar, Adrian Woiczechowski-Pop, Attila Bende, Ioana Georgeta Grosu, Natalia Miklášová, Elena Bogdan, Niculina D. Hădade, Anamaria Terec and Ion Grosu Tetrahedron Letters 2017, submitted.
Attended conferences
- Niculina D. Hădade - A short journey through the geometrical and thermodynamical space of supramolecular and Dynamic Adaptive Chemistry Diaspora în Cercetarea Științifică și Învățământul Superior din România, 25-28 April 2016, Timișoara, Romania (ORAL PRESENTATION).
- Andreea P. Diac, Alexandra Bogdan, Niculina D. Hădade, Ion Grosu - On the eve of the synthesis of a new photochemical molecular machine with conformational versatility, 27th European Colloquium on Heterocyclic Chemistry, 3-6 July, Amsterdam, Netherlands (POSTER).
- Levi Gabrian, Niculina D. Hădade, Anamaria Terec, Ion Grosu - An Approach Towards Obtaining some New Molecular Cages Containing Phenanthroline Derivatives as Side Arms, A XXXIV-a Conferinta Nationala de Chimie , 04-07 Octombrie 2016, Calimanesti-Caciulata (POSTER).
- Lidia Pop, Niculina D. Hădade, Ion Grosu - Charge-Assisted Hydrogen Bonding Self-Assembly of Bis-Amidine Complexes, A XXXIV-a Conferinta Nationala de Chimie , 04-07 Octombrie 2016, Calimanesti-Caciulata. (ORAL PRESENTATION)
- Andreea Diac, Lidia Pop, Niculina D. Hădade - Shape persistent aromatic diimide - based macrocycles: synthesis and supramolecular properties - 18th Tetrahedron Symposium, 27-30 June 2017, Budapest. (POSTER)
MSc Thesis
For information about unpublished results contact Dr. Niculina D. Hădade at nbogdan (at) chem.ubbcluj.ro.
- Sinteza și caracterizarea unor derivați ai 3,6-fluorenului – intermediari în obținerea de macrocicluri cu geometrie pătrată - Borbáth Boglárka
- Sinteza și caracterizarea unor derivați ai naftalendiimidei: intermediari cheie în obținerea de cuști 3D rigide – Maria Cristina Lupas
- Sinteza și analiza structurală a unor derivați de carbazol și naftalendiimidă - intermediari în sinteza de macrocicluri cu geometrie pătrată - Denisa Munteanu
- Sinteza și caracterizarea unor derivați ai 2,6-bis(aminometil)fenolului – intermediari în obținerea de macrocicluri cu structură hexagonal - Cristina Ozarciuc