Supramolecular Organic and Organometallic Chemistry Centre

Abstract
The anion exchange membranes (AEMs) remain plagued by either low stability in an alkaline environment or low ionic conductivities. This project proposes to overcome these challenges for water electrolysers and zinc-air batteries by the careful design of novel AEMs that take onto consideration both the chemical structure of polymer backbone and the cationic head group. The COFFEE project addresses these challenges by proposing a novel class of AEMs based on covalent organic frameworks (COFs) and Rubbery Organic Frameworks (ROFs) to promote enhanced membrane stability, conductivity, and selectivity. The development of durable, high-performance AEMs will push these developmental technologies closer to commercial viability and the successful commercialization of low-cost electrolyser and battery technologies will contribute to the widespread adoption of renewable energy solutions and directly support Europe's greenhouse gas emission reduction targets.

Objectives
The main objective of COFFEE is to develop a versatile platform of anion exchange membranes (AEMs), enabling highly durable, high-performance electrochemical energy conversion and storage devices. We designed these membranes to contain COFs, ROFs and pending ammonium cations in an ordered structure showing specific channels which enable the fast transport of anions having as result a high increasing of the performances of water electrolysers and Zn-air batteries.

Results 2022

In this first stage of our project (participation of the Romanian partner) two main activities were targeted: A.1.1. Synthesis of diagonal and trigonal building blocks decorated with formyl, ammine and acylhydrazide groups; A.1.2. Synthesis of tetragonal building blocks decorated with formyl, ammine and acylhydrazide groups [these two activities continue in 2023, too]. The synthesis of three building blocks [one diagonal (diacylhydryzide), one trigonal (triformyl) and one tetragonal (tetraformyl)] were successfully carried out and the compounds were obtained in large quantities in order to allow further experiments. The synthesis for other 6 important building blocks is undergoing, and the key intermediary products were already obtained. Two available building blocks were already used for the access to COF-ROF membranes, and the preliminary investigations of the obtained membranes revealed the expected properties (Figure 1). The obtained results were presented in one lecture at the Symposium 120 Years of the Birth of Academician C.D. Nenitescu and 4 communications (an oral presentation and three posters) at Conferința Națională de Chimie, Ediția XXXVI, 03–07 octombrie 2022, Călimănești – Căciulata, Vâlcea, România.

Results 2023

In the second stage of our project (participation of the Romanian partner) three main activities were targeted: A2.1. Synthesis of diagonal and trigonal building blocks (BB) decorated with formyl, ammine or acylhydrazide groups (continuation of stage I); A.2.2. Synthesis of tetragonal BBs decorated with formyl, ammine and acylhydrazide groups (continuation of stage I); A.2.3. Synthesis of and characterization of COFs and ROFs; The synthesis of 10 building blocks [8 digonal (5 with formyl and 3 with ammine groups), one trigonal (triformyl) and one tetragonal (tetraformyl)] were successfully carried out and 6 of the compounds were obtained in large quantities in order to allow further experiments. Five available building blocks were already used for the access to COF-ROF membranes and the investigations on the obtained membranes revealed in four cases the expected properties (Figure 2). These membranes were sent to our partners in France and Norway for further investigations. The results were presented in two lectures at KAUST Research Conference - February 13-16, 2023 (Dr. Niculina Hădade) and at Smart Diaspora 2023 - Exploratory workshop Transboundary chemistry at the forefront of molecular sciences” Timisoara 10-13 April 2023 (Prof. dr. Ion Grosu) and on a poster at 13th APMAS Congress, 11-17th October Oludeniz, Turkey (Prof. dr. Ion Grosu). Master students Ioan Stroia and Andreea Oanea participated at 19th International Conference Students for Students, Babes-Bolyai University, Cluj-Napoca, 26-30 aprilie 2023 with an oral presentations.

Dissemination

Conferences

1. KAUST Research Conference
   Niculina D. Hădade,
   Porous organic polymers as heterogeneous catalysts for cross-coupling reactions, Kaust, Germania, 13-16 february, 2023 (invited lecture).
   
   
2. „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).
   
   
3. 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).
   
   
4. 19th International Conference Students for Students
   Ioan Stroia, Florin Teleanu, Ionut-Tudor Moraru
   “Induced Magnetic Field in Carbon Nanorings: In-Plane Aromaticity/Antiaromaticity of [3]-[6]Cycloparaphenylenes” , Cluj-Napoca, România, 26-30 april, 2023 (oral presentation).
   
   
5. 19th International Conference Students for Students
   Andreea Oanea, Niculina Hădade, Elena Bogdan
   New N-aroylhydrazones as tunable photoswitches, Cluj-Napoca, România, 26-30 april, 2023 (oral presentation).
   
   

Articles

1. 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