Proiect PN-III-P4-PCE-2021-1812:
Project timespan
Project team
Abstract
Project objectives
Budget
Dissemination
Final activity report
Raport final de activitate
Title of project: Innovative COFs and hybrid metal@COF materials for smart applications: heterogeneous catalysis and Single Material Organic Solar Cells (SMOSCs)
Acronim:ICOFCOSC
Funding authority: Executive Agency for Higher Education, Research, Development and Innovation Funding (UEFISCDI)
Contract: 111 / 09.06.2022
Research Team:
- Prof. Dr. Ion Grosu (Corresponding Member of the Romanian Academy) - Project leader
- Assoc. Prof. Dr. Anamaria Terec - Senior researcher
- Assoc. Prof. Dr. Lorant Andras Szolga - Senior researcher
- Lecturer Dr. Andreea Petronela Crişan - Senior researcher
- Dr. Ioana Georgeta Grosu - Senior researcher
- Dr. Natalia Terenti - Postdoctoral researcher
- Dr. Alexandra Bogdan - Postdoctoral researcher
- PhD Student Gavril-Ionel Giurgi
- PhD Student Alexia Mihaela Frincu
- Dr. Natalia Terenti - Postdoctoral researcher
- Dr. Alexandra Bogdan - Postdoctoral researcher
- PhD Student Cristina Cociug
- PhD Student Alexandru Bărbănțan
Project timespan
2022 -- 2024
2022 -- 2024
Abstract
Covalent organic frameworks (COFs) emerged as promising porous, crystalline materials that found various many applications in various fields. The proposed project focuses on the obtaining and characterization of COFs and Metal@COF (Me@COF) hybrid materials designed for innovative applications in heterogenous catalysis, chiral separations and active materials in state-of-the-art Single Material Organic Solar Cells (SMOSCs). The strengths of the proposal rely on the careful design of the targeted materials. Therefore, versatile building blocks of various geometries are used to give access to a plethora of 3D achiral and chiral COFs and Me@COFs with modulable pore size to act as catalysts and asymmetric catalysts for various cross-coupling reactions. The main advantage of the proposed materials is the direct access to Me@COF hybrid materials by coupling reactions (i.e. Suzuki-Miyaura, Sonogashira, Glaser), thus incorporating in the COF structure the metal used as a catalyst in their synthesis. In addition, macrocycles- and cryptand-based COFs and Me@COFs bearing different types of cavities and catalytic site will be obtained and tested as multifunctional catalysts for reaction carried out sequentially or in cascade. Furthermore, taking advantage of highly ordered COFs structures we propose 2D frameworks that display efficient segregation of the donor and acceptor units, a requirement in the fabrication of highly efficient and stable SMOSCs.
Covalent organic frameworks (COFs) emerged as promising porous, crystalline materials that found various many applications in various fields. The proposed project focuses on the obtaining and characterization of COFs and Metal@COF (Me@COF) hybrid materials designed for innovative applications in heterogenous catalysis, chiral separations and active materials in state-of-the-art Single Material Organic Solar Cells (SMOSCs). The strengths of the proposal rely on the careful design of the targeted materials. Therefore, versatile building blocks of various geometries are used to give access to a plethora of 3D achiral and chiral COFs and Me@COFs with modulable pore size to act as catalysts and asymmetric catalysts for various cross-coupling reactions. The main advantage of the proposed materials is the direct access to Me@COF hybrid materials by coupling reactions (i.e. Suzuki-Miyaura, Sonogashira, Glaser), thus incorporating in the COF structure the metal used as a catalyst in their synthesis. In addition, macrocycles- and cryptand-based COFs and Me@COFs bearing different types of cavities and catalytic site will be obtained and tested as multifunctional catalysts for reaction carried out sequentially or in cascade. Furthermore, taking advantage of highly ordered COFs structures we propose 2D frameworks that display efficient segregation of the donor and acceptor units, a requirement in the fabrication of highly efficient and stable SMOSCs.
Objectives
The main objective of the project is the synthesis and characterization of innovative COFs and Me@COFs materials for application as heterogenous catalysts with improved properties as well as highly ordered COFs showing segregation of donor and acceptor units for the fabrication of SMOSCs with higher efficiency.
The specific objectives are:
O1. Rational design of COFs and access to COFs and Me@COFs hybrid materials (achiral) with targeted high catalytic activity and selectivity;
O2. Synthesis, characterization and applications of achiral COFs and Me@COFs hybrid materials for heterogeneous catalysis;
O3. Synthesis and characterization of selected chiral COFs and Me@COFs hybrid materials and the development of innovative applications in asymmetric synthesis and chiral separations;
O4. Synthesis of donor and acceptor-based COFs, fabrication and characterization of Single Material Organic Solar Cells - based COFs;
O5. Development of material and human resources for research;
O6. Dissemination of the results.
The main objective of the project is the synthesis and characterization of innovative COFs and Me@COFs materials for application as heterogenous catalysts with improved properties as well as highly ordered COFs showing segregation of donor and acceptor units for the fabrication of SMOSCs with higher efficiency.
The specific objectives are:
O1. Rational design of COFs and access to COFs and Me@COFs hybrid materials (achiral) with targeted high catalytic activity and selectivity;
O2. Synthesis, characterization and applications of achiral COFs and Me@COFs hybrid materials for heterogeneous catalysis;
O3. Synthesis and characterization of selected chiral COFs and Me@COFs hybrid materials and the development of innovative applications in asymmetric synthesis and chiral separations;
O4. Synthesis of donor and acceptor-based COFs, fabrication and characterization of Single Material Organic Solar Cells - based COFs;
O5. Development of material and human resources for research;
O6. Dissemination of the results.
Project budget
| Nr | Category | Budget (RON) | |||
|---|---|---|---|---|---|
| 2022 | 2023 | 2024 | TOTAL | ||
| 1 | Personnel costs | 80000 | 310000 | 300000 | 690000 |
| 2 | Logistics exhibiting | 120756 | 99390 | 52854 | 273000 |
| - equipments | 93000 | 0 | 0 | 93000 | |
| - materials | 27756 | 99390 | 52854 | 180000 | |
| 3 | Travel | 2000 | 15000 | 13000 | 30000 |
| 4 | Indirect costs | 25244 | 97610 | 84146 | 207000 |
| 5 | TOTAL | 228000 | 522000 | 450000 | 1200000 |
Results 2022
First Stage: Synthesis and characterization of building blocks and elaboration of the procedures for the access to COFs and Me@COF hybrid materials for heterogenous catalysts and SMOSCs.
First Stage: Synthesis and characterization of building blocks and elaboration of the procedures for the access to COFs and Me@COF hybrid materials for heterogenous catalysts and SMOSCs.
Description
Activity 1.1. Synthesis and characterization of building blocks.
The design and synthesis of tetrahedral (4 types), tetragonal (3 types), trigonal (4 types) and digonal (3 types) building blocks for COFs dedicated to applications in catalysis and for SMOSCs were performed. The 14 building blocks were characterized by NMR and MS spectra.
Activity 1.2. Elaboration of the procedures for the access to COFs and hybrid Me@COF materials for catalysis and for the access to SMOSCs.
Three COFs were obtained by a DCC method based on imine formation reactions. The method was solvothermal and the optimal conditions were found by varying the solvents, temperature and reaction time. The COFs were dopped with Pd(OAc)2 in DCM and then Pd(2+) was reduced to Pd(0) resulting hybrid Me@COF materials which were used successfully to catalyze Suzuki-Miyaura cross coupling reactions. An exciting COF was obtained via boronic ester type connections and this COF catalyzed the click reaction in a purely metal free process.
Activity 1.1. Synthesis and characterization of building blocks.
The design and synthesis of tetrahedral (4 types), tetragonal (3 types), trigonal (4 types) and digonal (3 types) building blocks for COFs dedicated to applications in catalysis and for SMOSCs were performed. The 14 building blocks were characterized by NMR and MS spectra.
Activity 1.2. Elaboration of the procedures for the access to COFs and hybrid Me@COF materials for catalysis and for the access to SMOSCs.
Three COFs were obtained by a DCC method based on imine formation reactions. The method was solvothermal and the optimal conditions were found by varying the solvents, temperature and reaction time. The COFs were dopped with Pd(OAc)2 in DCM and then Pd(2+) was reduced to Pd(0) resulting hybrid Me@COF materials which were used successfully to catalyze Suzuki-Miyaura cross coupling reactions. An exciting COF was obtained via boronic ester type connections and this COF catalyzed the click reaction in a purely metal free process.
Dissemination
Conferences
Conferences
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Sympozium: 120 de ani de la nașterea Academicianului Costin D. Nenițescu,
Ion Grosu,
The Exciting Journey From Stereochemistry to Host-molecules, Self-assembled Supramolecular Architectures and Organic Molecules with Smart Applications, Bucuresti, România, 22-23 September, 2022 (invited lecture).
-
Conferința Națională de Chimie, Ediția XXXVI,
Cyril Nicolay, Ion Grosu, Niculina D. Hădade,
A New Copper(I)-N-Heterocyclic Carbene-Based Porous Organic Material as Heterogenous Catalyst for Carbon-Nitrogen Coupling Reaction, Călimănești – Căciulata, Vâlcea, România, 03-07 October, 2022 (oral presentation).
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Conferința Națională de Chimie, Ediția XXXVI,
Daniel-Florin Bogoșel, Andreea Petronela Crișan, Anamaria Terec, Ion Grosu,
Small π-Conjugated Systems Based on Triarylamine Derivatives as Potential Materials for Single-Component Organic Solar Cells, Călimănești – Căciulata, Vâlcea, România, 03-07 October, 2022 (oral presentation).
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Exploring the optoelectronic properties of D-A and A-D-A 2,2’-bi[3,2-b]thienothiophene derivatives,
Levi Gabrian, Gavril-Ionel Giurgi, Ioan Stroia, Elena Bogdan, Andreea Petronela Crişan*, Niculina Daniela Hădade, Ion Grosu and Anamaria Terec *,
Molecules,2022, 14, 8463.
DOI: 10.3390/molecules27238463
Results 2023
Second Stage: Synthesis and characterization of COFs and hybrid materials Me@COF for 3D heterogenous catalysts and SMOSCs (2D) and the investigation of their applications
Second Stage: Synthesis and characterization of COFs and hybrid materials Me@COF for 3D heterogenous catalysts and SMOSCs (2D) and the investigation of their applications
Description
Activity 2.1. Synthesis and characterization of building blocks (continuation of stage 1)
The design and synthesis of tetrahedral (2 types), tetragonal (2 types), trigonal (3 types) and digonal (4 types) building blocks for COFs dedicated to applications in catalysis and for SMOSCs. The 11 building blocks were characterized by NMR and MS spectra. It is to underline the obtaining of the chiral BB (S configuration); a di-yne of binaphthyl which was used for the access to Pd@Cu@PAF-CHIR1 hybrid material.
Activity 2.2. Synthesis, characterization and investigation of catalytical activity of COFs and hybrid Me@COF materials designed for heterogenous catalysis
The one-step synthesis of three hybrid Pd@Cu@PAF materials by the Sonogashira cross-coupling reaction starting from tetrahalogenated tetrahedral (or pseudotetrahedral) substrates and aromatic di-ynes were successfully carried out. The hybrid Pd@Cu@PAF materials were powerful multifunctional catalysts for Suzuki-Miyaura and Sonogashira cross-coupling and „click” reactions, as well as for one-pot “click”-Sonogashira procedures. COFs and PAFs (Porous Aromatic Frameworks; the differences between COFs and PAFs are due to the higher crystallinity of COFs) were characterized by specific measurements (TEM, XPR, BET) and for the catalytic studies were elaborated specific procedures.
Activity 2.3. Synthesis, characterization and investigation of photovoltaic activity of 2D COFs designed for the access to SMOSCs.
Two COF-OSCs were obtained by Knoevenagel condensation reactions. These COFs include donor and acceptor units in their structures. The SMOSCs obtained with these COFs revealed remarkable efficiencies for such materials (unexplored). 2D COFs were characterized by specific measurements (TEM, XPR, BET) and for the fabrication of SMOSCs were elaborated specific procedures
Activity 2.1. Synthesis and characterization of building blocks (continuation of stage 1)
The design and synthesis of tetrahedral (2 types), tetragonal (2 types), trigonal (3 types) and digonal (4 types) building blocks for COFs dedicated to applications in catalysis and for SMOSCs. The 11 building blocks were characterized by NMR and MS spectra. It is to underline the obtaining of the chiral BB (S configuration); a di-yne of binaphthyl which was used for the access to Pd@Cu@PAF-CHIR1 hybrid material.
Activity 2.2. Synthesis, characterization and investigation of catalytical activity of COFs and hybrid Me@COF materials designed for heterogenous catalysis
The one-step synthesis of three hybrid Pd@Cu@PAF materials by the Sonogashira cross-coupling reaction starting from tetrahalogenated tetrahedral (or pseudotetrahedral) substrates and aromatic di-ynes were successfully carried out. The hybrid Pd@Cu@PAF materials were powerful multifunctional catalysts for Suzuki-Miyaura and Sonogashira cross-coupling and „click” reactions, as well as for one-pot “click”-Sonogashira procedures. COFs and PAFs (Porous Aromatic Frameworks; the differences between COFs and PAFs are due to the higher crystallinity of COFs) were characterized by specific measurements (TEM, XPR, BET) and for the catalytic studies were elaborated specific procedures.
Activity 2.3. Synthesis, characterization and investigation of photovoltaic activity of 2D COFs designed for the access to SMOSCs.
Two COF-OSCs were obtained by Knoevenagel condensation reactions. These COFs include donor and acceptor units in their structures. The SMOSCs obtained with these COFs revealed remarkable efficiencies for such materials (unexplored). 2D COFs were characterized by specific measurements (TEM, XPR, BET) and for the fabrication of SMOSCs were elaborated specific procedures
Dissemination
Conferences
Conferences
-
„Smart Diaspora 2023 - Exploratory workshop Transboundary chemistry at the forefront of molecular sciences”
Ion Grosu,
An Exciting Journey From Stereochemistry to Host-molecules, Self-assembled Supramolecular Architectures and Organic Molecules with Smart Applications, Timisoara, România, 10-13 April, 2023 (invited lecture).
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13th APMAS Congress
Ion Grosu, Natalia Terenti, Lidia Căta, Cristina Cociug, Niculina D. Hădade,
“Hybrid METAL@PAF materials as smart catalysts for cross-coupling and “click” reactions”, Oludeniz, Turkey, 11-17 October, 2023 (poster presentation).
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13th APMAS Congress
Ioana G. Grosu, Lidia Căta (Pop), Maria Miclăuş, Cristina Cociug, Alexandru Bărbănţan, Anamaria Terec, Ion Grosu, Niculina D. Hădade
Supramolecular and covalent organic frameworks based on 9,9’-spirobifluorene building blocks, Oludeniz, Turkey, 11-17 October, 2023 (poster presentation).
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Exploring the optoelectronic properties of D-A and A-D-A 2,2’-bi[3,2-b]thienothiophene derivatives,
Ioan Stroia, Mӑdӑlina Elena Moisӑ, Alexandra Pop, Baptiste Legrand,c Anamaria Hanganu, Niculina Daniela Hӑdade, Ion Grosu ,
Molecules, 2022, 14, 8463.
DOI: 10.1021/acsami.1c24429
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Planar Chiral p,p’-Terphenyl-based Cyclophanes with Remarkable Enantiomers Stability: Synthesis, Theoretical Investigations and Complexation Studies;
Cătălin C. Anghel, Teodor A. Cucuiet, Niculina D. Hădade, and Ion Grosu
J. Org. Chem., 2023, 88 (22), 15647-15657.
DOI: 10.1021/acs.joc.3c01631
For the J. Org. Chem. publication we proposed a “Cover” which was accepted and it is a “logo” of issue 22
Results 2024
Third Stage: Synthesis, characterization, and investigation of improved 3D materials (COFs and hybrid Me@COF) for achiral and chiral heterogeneous catalysts and of 2D COFs for SMOSCs with enhanced performances.
Third Stage: Synthesis, characterization, and investigation of improved 3D materials (COFs and hybrid Me@COF) for achiral and chiral heterogeneous catalysts and of 2D COFs for SMOSCs with enhanced performances.
Description
Activity 3.1. Synthesis, characterization, and investigation of the catalytical activity of COFs and hybrid Me@COF materials designed for heterogeneous catalysis (continuation of stage 2)
New hybrid Pd@Cu@PAF catalysts were obtained starting from unexplored trispirobifluorene building blocks by the already classical one-step preparation of such materials using the Sonogashira cross-coupling of a tetrahalogenated trispirobifluorene derivative with diethynylpyrene. This new catalyst with larger cavities were used to catalyze cross-coupling reactions (e.g. Suzuki-Miyaura). Pd@Cu(I)@PAF-SP catalyst was successfully used for the synthesis of macrocycles by the “click” reaction of a linear azido-alkyne.
Activity 3.2. Synthesis, characterization, and investigation of the photovoltaic activity of 2D COFs designed for access to SMOSCs
Several 2D COFs were obtained using new building blocks with better donor or acceptor properties (for OSC) in order to improve the PCE (Power Conversion Efficiency) values of the COF-OSC devices. Among these new platforms, benzotrithiophene, tris(benzothiadiazole), and bis(indandione) derivatives were used. The deposition of these COFs on the ITO support was very difficult and we had to reset the design of COFOSC targets again.
Activity 3.3. Synthesis, characterization, and investigation of catalytic and photovoltaic activity of COFs and hybrid Me@COF improved materials for heterogeneous catalysis and the obtaining of SMOSCs with higher performances
For hybrid Pd@Cu(I)@PAF materials employed as catalysts for cross-coupling reactions, the main problem was to increase the size of the cavities inside the porous materials. This problem was solved by using trispirobifluorene tetrahalogenated derivatives instead of spirobifluorene ones and by expanding the di-ynes with phenylene or ethynylphenylene spacers. For COFOSCs the main problem was to increase the usually low solubility of the COFs. We obtained COFs with improved solubility by using aldehydes and cyanomethyl derivatives decorated with alkyl or alkyloxy groups instead of the classic building blocks which don’t exhibit such groups.
Activity 3.4 Synthesis, characterization, and investigation of the catalytical activity of COFs and hybrid Me@COF materials designed for heterogeneous asymmetric catalysis
Chiral Pd@Cu(I)PAF catalysts were obtained starting from enantiomerically pure di-ynes with binaphthyl units and tetraiodurated spirobifluorene building blocks by Sonogashira cross-coupling reactions. The reactive alkyne groups were connected directly to the binaphthyl unit or via ethynylphenylene spacers. The chiral hybrid materials are designed to catalyse the asymmetric synthesis of atropoisomer chiral auxiliaries by cross-coupling reactions. The first tests with these catalysts revealed the formation of biphenyl derivatives by Suzuki-Miyaura cross-coupling reactions. The investigation of the enantioselectivity of these reactions is under evaluation.
Activity 3.1. Synthesis, characterization, and investigation of the catalytical activity of COFs and hybrid Me@COF materials designed for heterogeneous catalysis (continuation of stage 2)
New hybrid Pd@Cu@PAF catalysts were obtained starting from unexplored trispirobifluorene building blocks by the already classical one-step preparation of such materials using the Sonogashira cross-coupling of a tetrahalogenated trispirobifluorene derivative with diethynylpyrene. This new catalyst with larger cavities were used to catalyze cross-coupling reactions (e.g. Suzuki-Miyaura). Pd@Cu(I)@PAF-SP catalyst was successfully used for the synthesis of macrocycles by the “click” reaction of a linear azido-alkyne.
Activity 3.2. Synthesis, characterization, and investigation of the photovoltaic activity of 2D COFs designed for access to SMOSCs
Several 2D COFs were obtained using new building blocks with better donor or acceptor properties (for OSC) in order to improve the PCE (Power Conversion Efficiency) values of the COF-OSC devices. Among these new platforms, benzotrithiophene, tris(benzothiadiazole), and bis(indandione) derivatives were used. The deposition of these COFs on the ITO support was very difficult and we had to reset the design of COFOSC targets again.
Activity 3.3. Synthesis, characterization, and investigation of catalytic and photovoltaic activity of COFs and hybrid Me@COF improved materials for heterogeneous catalysis and the obtaining of SMOSCs with higher performances
For hybrid Pd@Cu(I)@PAF materials employed as catalysts for cross-coupling reactions, the main problem was to increase the size of the cavities inside the porous materials. This problem was solved by using trispirobifluorene tetrahalogenated derivatives instead of spirobifluorene ones and by expanding the di-ynes with phenylene or ethynylphenylene spacers. For COFOSCs the main problem was to increase the usually low solubility of the COFs. We obtained COFs with improved solubility by using aldehydes and cyanomethyl derivatives decorated with alkyl or alkyloxy groups instead of the classic building blocks which don’t exhibit such groups.
Activity 3.4 Synthesis, characterization, and investigation of the catalytical activity of COFs and hybrid Me@COF materials designed for heterogeneous asymmetric catalysis
Chiral Pd@Cu(I)PAF catalysts were obtained starting from enantiomerically pure di-ynes with binaphthyl units and tetraiodurated spirobifluorene building blocks by Sonogashira cross-coupling reactions. The reactive alkyne groups were connected directly to the binaphthyl unit or via ethynylphenylene spacers. The chiral hybrid materials are designed to catalyse the asymmetric synthesis of atropoisomer chiral auxiliaries by cross-coupling reactions. The first tests with these catalysts revealed the formation of biphenyl derivatives by Suzuki-Miyaura cross-coupling reactions. The investigation of the enantioselectivity of these reactions is under evaluation.
Dissemination
Conferences
Conferences
-
14th International Advances in Applied Physics & Materials Science Congress & Exhibition (APMAS)
Ion Grosu, Natalia Terenti, Alexia M. Frîncu, Daniel F. Bogoşel, Cyril Nicolay, Gavril.-I. Giurgi, Andreea P. Crişan, Anamaria Terec, Niculina D. Hădade,
Covalent Organic Frameworks for Homojunction SMOSCs and Electrode Materials, Oludeniz, Turkey , 8-14 October, 2024 (poster presentation).
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14th International Advances in Applied Physics & Materials Science Congress & Exhibition (APMAS)
Ioana G. Grosu, Alexandru Bărbănţan , Maria Miclăuş
Novel 9,9’-Dispiro- and Trispirobifluorene Building Blocks for the Access to Smart Supramolecular and Covalent Organic Frameworks, Oludeniz, Turkey, 8-14 October, 2024 (poster presentation).
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Belgian Organic Synthesis Symposium (BOSS), XVIII
Alexia M. Frîncu, Natalia Terenti, Gavril I. Giurgi, Andreea P. Crişan, Anamaria Terec, Ion Grosu,
Synthesis and Investigation of Porous Organic Polymers Based on Donor-Acceptor Units as Active Layers in Organic Solar Cells, Liege, Belgium, 30 june-05 july, 2024 (poster presentation).
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Suzuki-Miyaura, Sonogashira cross-coupling and CuAAC reactions suite for the access to a large macrocycle with m,m’-terphenyl motif,
Eszter Lakatos, Niculina D. Hădade, Elena Bogdan, Anamaria Terec, Ion Grosu,
Revue Roumaine de Chimie, 2024, 69, 255-262.
DOI: 10.33224/rrch.2024.69.5-6.03
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The Impact of Structural Modifications in Donor-Acceptor Systems on Homojunction Organic Solar Cell Photovoltaic Properties,
Daniel F. Bogoșel, Gavril I. Giurgi, Alexandru Balan, Alexandra M. Pop, Ion Grosu, Andreea P. Crișan, Anamaria Terec
Organic Electronics (accepted with revisions; ORGELE-D-24-00416),
Final activity report
PN-III-P4-PCE-2021-1812
Project's results
The research within this project was focused on two main directions – one dedicated to the heterogenous catalysis of cross-coupling reactions mediated by original Metal@COF (Metal@PAF) catalysts and another in which we elaborated simple OSC (Organic Solar Cells) based on original COF-2D materials to act as SMOSCs-uri (Single-Material Organic Solar Cell).
Coupling reactions (with the formation of C-C bonds) are pivotal to the development of organic chemistry and the creation of new sophisticated molecules that find many applications in the most important and of interest fields such as the pharmaceutical industry (creation of new and powerful drugs). Coupling reactions are usually very expensive because they require organometallic catalysts with complex structures and challenging synthesis and, in most cases, they cannot be recycled. In addition, asymmetric synthesis requires chiral auxiliaries (enantiomerically pure compounds) which are even more expensive and sensitive. The hybrid Metal@PAF catalysts obtained in this project are recyclable and ensure a facile purification of the final compounds. In addition, the chiral Metal@PAF catalysts show high enantiomerical stability and no racemization processes occur. These new catalysts promise a relevant reduction of the prices for the chemical products that involve (asymmetric) cross-coupling reactions in their synthesis, including drugs that are of large interest to many people.
SMOSCs (Single Material Organic Solar Cells) are a promising solution for the simplification in the fabrication of organic solar cells and an important reduction of their costs which will make them competitive to the classical (commercial) silicon-based solar cells. OSCs bring many other advantages, as they are lightweight, friendly with the environment (can be recycled easier), transparent (e.g. they can be applied on windows), and the procedures involved in their fabrication are less complicated.
The access to SMOSCs based on 2D COFs is tempting because these materials are more robust, they can be obtained by simpler fabrication procedures and they are a remarkable future solution for producing large amounts of cheap and green energy.
In this project, we obtained and investigated several COF-SMOSCs. Their syntheses were carried out by Knoevenagel condensation reactions of di- or trialdehydes with tri-or dicyanomethylarenes. These COF-SMOSCs were used for the fabrication of solar cells. Despite the quite small efficiencies of these COF-SMOSCs cells (less than 1%), in this project we proved that 2D COFs can be used for the fabrication of solar cells and we elaborated procedures for the synthesis of COFs and for the fabrication and investigation of the solar cells.
The dissemination of the results was carried out via 5 papers (J. Org. Chem., Beil. J. Org. Chem., Molecules, Rev. Roum. Chim. and Org. Electron.) and the participation with 10 works at national and international conferences.
PN-III-P4-PCE-2021-1812
Project's results
The research within this project was focused on two main directions – one dedicated to the heterogenous catalysis of cross-coupling reactions mediated by original Metal@COF (Metal@PAF) catalysts and another in which we elaborated simple OSC (Organic Solar Cells) based on original COF-2D materials to act as SMOSCs-uri (Single-Material Organic Solar Cell).
Coupling reactions (with the formation of C-C bonds) are pivotal to the development of organic chemistry and the creation of new sophisticated molecules that find many applications in the most important and of interest fields such as the pharmaceutical industry (creation of new and powerful drugs). Coupling reactions are usually very expensive because they require organometallic catalysts with complex structures and challenging synthesis and, in most cases, they cannot be recycled. In addition, asymmetric synthesis requires chiral auxiliaries (enantiomerically pure compounds) which are even more expensive and sensitive. The hybrid Metal@PAF catalysts obtained in this project are recyclable and ensure a facile purification of the final compounds. In addition, the chiral Metal@PAF catalysts show high enantiomerical stability and no racemization processes occur. These new catalysts promise a relevant reduction of the prices for the chemical products that involve (asymmetric) cross-coupling reactions in their synthesis, including drugs that are of large interest to many people.
SMOSCs (Single Material Organic Solar Cells) are a promising solution for the simplification in the fabrication of organic solar cells and an important reduction of their costs which will make them competitive to the classical (commercial) silicon-based solar cells. OSCs bring many other advantages, as they are lightweight, friendly with the environment (can be recycled easier), transparent (e.g. they can be applied on windows), and the procedures involved in their fabrication are less complicated.
The access to SMOSCs based on 2D COFs is tempting because these materials are more robust, they can be obtained by simpler fabrication procedures and they are a remarkable future solution for producing large amounts of cheap and green energy.
In this project, we obtained and investigated several COF-SMOSCs. Their syntheses were carried out by Knoevenagel condensation reactions of di- or trialdehydes with tri-or dicyanomethylarenes. These COF-SMOSCs were used for the fabrication of solar cells. Despite the quite small efficiencies of these COF-SMOSCs cells (less than 1%), in this project we proved that 2D COFs can be used for the fabrication of solar cells and we elaborated procedures for the synthesis of COFs and for the fabrication and investigation of the solar cells.
The dissemination of the results was carried out via 5 papers (J. Org. Chem., Beil. J. Org. Chem., Molecules, Rev. Roum. Chim. and Org. Electron.) and the participation with 10 works at national and international conferences.
Raport fnal de activitate
PN-III-P4-PCE-2021-1812
Rezultate proiectului
Acest proiect a abordat două subiecte extrem de importante, unul legat de realizarea unor reacții de cuplare în cataliza eterogenă folosind niște catalizatori originali de tipul Metal@PAF (Metal@COF) și altul corelat cu obținerea unor celule solare cu o structură simplificată bazată pe materiale originale de tip COF 2D care să funcționeze ca SMOSCs-uri (Single Material Organic Solar Cell).
Reacțiile de cuplare (cele în care se formează noi legături C-C) sunt motorul dezvoltării chimiei organice și a accesului la noi molecule cu grad ridicat de elaborare și cu multiple aplicații printre cele mai importante și de interes fiind cele din industria farmaceutică. Reacțiile de cuplare implică costuri foarte mari deoarece ele necesită de cele mai multe ori catalizatori organometalici cu o structură extrem de complexă și care de cele mai multe ori sunt nereciclabili. Sintezele asimetrice implică în plus auxiliari chirali (molecule enantiomeric pure) care au un cost și mai ridicat.
Materialele Metal@PAF obținute în acest proiect sunt robuste, sunt reciclabile și purificarea produșilor de reacție este mult simplificată. Catalizatorii chirali obținuți în acest proiect sunt foarte stabili enantiomeric și nu racemizează. Acești catalizatori promit o reducere substanțială a costurilor pentru procesele în care vor fi implicați și vor conduce implicit la ieftinirea unor produse esențiale cum ar fi medicamentele în a căror sinteză vor fi implicați.
SMOSCs-urile (Single Material Organic Solar Cell) promit o simplificare majoră a construcției OSC și o reducere a costurilor de fabricare a acestora făcându-le rentabile în raport cu cele clasice pe baza de siliciu. OSC-urile în raport cu celulele solare clasice (cu Si) sunt mult mai ușoare, sunt mult mai prietenoase cu mediu (mai ușor de reciclat), sunt transparente (se pot instala pe geamuri), se obțin mai ușor și, în perspectivă, pot deveni mai ieftine decât cele clasice. Obținerea de SMOSCs pe bază de COF-uri 2D este o variantă tentantă deoarece oferă SMOSCs-uri mai robuste și mai ușor de fabricat care pot avea un impact important în producerea mai ieftin a unei cantități mari de energie verde. In acest proiect am obținut și am investigat astfel de COF-SMOSCs-uri.
Sintezele au fost realizate prin reacții de condensare Knoevenagel folosind trialdehide și di- sau tricianometil arene. Aceste COF-SMOSCs-uri au fost folosite la fabricarea de materiale care au prezentat proprietăți de celule solare. Chiar dacă eficiența acestor celule este mică (sub 1%), prin acest proiect am dovedit că astfel de materiale pot fi celule solare și am elaborat metode de sinteză, de depunere și de investigare a acestora.
Diseminarea rezultatelor s-a făcut prin publicarea a 5 articole (J. Org. Chem., Beil. J. Org. Chem., Molecules, Rev. Roum. Chim. și Org. Electron.) și prin participarea cu 10 lucrări științifice la conferințe de specialitate din țară sau străinătate.
PN-III-P4-PCE-2021-1812
Rezultate proiectului
Acest proiect a abordat două subiecte extrem de importante, unul legat de realizarea unor reacții de cuplare în cataliza eterogenă folosind niște catalizatori originali de tipul Metal@PAF (Metal@COF) și altul corelat cu obținerea unor celule solare cu o structură simplificată bazată pe materiale originale de tip COF 2D care să funcționeze ca SMOSCs-uri (Single Material Organic Solar Cell).
Reacțiile de cuplare (cele în care se formează noi legături C-C) sunt motorul dezvoltării chimiei organice și a accesului la noi molecule cu grad ridicat de elaborare și cu multiple aplicații printre cele mai importante și de interes fiind cele din industria farmaceutică. Reacțiile de cuplare implică costuri foarte mari deoarece ele necesită de cele mai multe ori catalizatori organometalici cu o structură extrem de complexă și care de cele mai multe ori sunt nereciclabili. Sintezele asimetrice implică în plus auxiliari chirali (molecule enantiomeric pure) care au un cost și mai ridicat.
Materialele Metal@PAF obținute în acest proiect sunt robuste, sunt reciclabile și purificarea produșilor de reacție este mult simplificată. Catalizatorii chirali obținuți în acest proiect sunt foarte stabili enantiomeric și nu racemizează. Acești catalizatori promit o reducere substanțială a costurilor pentru procesele în care vor fi implicați și vor conduce implicit la ieftinirea unor produse esențiale cum ar fi medicamentele în a căror sinteză vor fi implicați.
SMOSCs-urile (Single Material Organic Solar Cell) promit o simplificare majoră a construcției OSC și o reducere a costurilor de fabricare a acestora făcându-le rentabile în raport cu cele clasice pe baza de siliciu. OSC-urile în raport cu celulele solare clasice (cu Si) sunt mult mai ușoare, sunt mult mai prietenoase cu mediu (mai ușor de reciclat), sunt transparente (se pot instala pe geamuri), se obțin mai ușor și, în perspectivă, pot deveni mai ieftine decât cele clasice. Obținerea de SMOSCs pe bază de COF-uri 2D este o variantă tentantă deoarece oferă SMOSCs-uri mai robuste și mai ușor de fabricat care pot avea un impact important în producerea mai ieftin a unei cantități mari de energie verde. In acest proiect am obținut și am investigat astfel de COF-SMOSCs-uri.
Sintezele au fost realizate prin reacții de condensare Knoevenagel folosind trialdehide și di- sau tricianometil arene. Aceste COF-SMOSCs-uri au fost folosite la fabricarea de materiale care au prezentat proprietăți de celule solare. Chiar dacă eficiența acestor celule este mică (sub 1%), prin acest proiect am dovedit că astfel de materiale pot fi celule solare și am elaborat metode de sinteză, de depunere și de investigare a acestora.
Diseminarea rezultatelor s-a făcut prin publicarea a 5 articole (J. Org. Chem., Beil. J. Org. Chem., Molecules, Rev. Roum. Chim. și Org. Electron.) și prin participarea cu 10 lucrări științifice la conferințe de specialitate din țară sau străinătate.