Supramolecular Organic and Organometallic Chemistry Centre

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.

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.

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.

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.

Dissemination

Conferences

1. 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).
   
   
2. 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).
   
   
3. 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).
   
   

Articles

1. 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,under evaluation.