resumo
A three-component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation-inducing COF precursor and the diamines o-phenylenediamine (Ph), 2,3-diaminonaphthalene (Naph), or (1R,2R)-(+)-1,2-diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11-hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene-fused azaacene, i.e., Aza-COF series with full conversion of the dione moiety, long-range order, and high surface area. In addition, the novel three-component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza-COFs with nanostructured surfaces on various substrates. The Aza-COFs exhibit light absorption maxima in the blue spectral region, and each Aza-COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza-Ph- and Aza-Naph-COFs suggest ultrafast relaxation dynamics of excited-states within these COFs.
palavras-chave
THIN-FILMS
categoria
Chemistry
autores
Frey, L; Oliveira, O; Sharma, A; Guntermann, R; Fernandes, SPS; Cid-Seara, KM; Abbay, H; Thornes, H; Rocha, J; Döblinger, M; Kowalczyk, T; Rao, A; Salonen, LM; Medina, DD
nossos autores
João Rocha
Prof. CatedráticoProjectos
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
Supported Covalent Organic Frameworks for the Monitoring of Pharmaceutical Pollutants (Charm)
agradecimentos
The authors are grateful for financial support from the Free State of Bavaria through the Research Network "Solar Technologies go Hybrid", the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) in the COORNETs SPP 1928 Project ME 4515/1-2 and the Excellence Clusters "Nanosystems Initiative Munich (NIM)". O.O. acknowledges FCT-Fundacao para a Ciencia e Tecnologia for the Ph.D. scholarship SFRH/BD/141865/2018 and (with J.R.) funding to CICECO-Aveiro Institute of Materials (UIDB/50011/2020, UIDP/50011/2020 and LA/P/0006/2020). This work received funding through the Charm project (PTDC/QUI-OUT/2095/2021) through the FCT. H.A., H.T., and T.K. acknowledge a U.S. National Science Foundation CAREER award (DMR-1848067). A.S. and A.R. acknowledge support from the Engineering and Physical Sciences Research Council (UK) via grant EP/V055127/1. L.M.S. acknowledges financial support from the Spanish Ministry of Science and Innovation through the Ramon y Cajal grant RYC2020-030414-I. We acknowledge Dr. Steffen Schmidt for the preparation of the SEM images.