abstract
Vinylene-linked covalent organic frameworks (COFs) are typically prepared via the Knoevenagel reaction under acid- or base-catalyzed solvothermal or benzoic anhydride-catalyzed solid-state conditions under reaction times spanning from 3 to 5 days. Herein, we show that the incorporation of a dipole moment into the COF building block accelerates the formation of ordered material. Under solvent-free Knoevenagel conditions, 3,8-dimethyl-4,7-phenanthroline (Phen) in combination with C3-symmetric aldehydes gives access to ordered hexagonal vinylene-linked COFs. A detailed study using triformylbenzene as counterpart evidences the formation of crystalline framework within hours. Theoretical and experimental studies indicate that the fast formation stems from favorable intermolecular interactions of the pi-extended Phen building block due to the presence of a dipole moment, which also endows the material with excellent mechanical stability under ball milling. In addition, all prepared materials exhibited broad visible light absorption and narrow band gap energies of <= 2.48 eV and revealed photocatalytic activity for the degradation of dyes.
keywords
PHASE SYNTHESIS; SINGLET OXYGEN; DEGRADATION; CRYSTALLINE; ABSORPTION; PRINCIPLES; SPECTRA; DESIGN
subject category
Chemistry; Materials Science
authors
Ponte, C; Prieto, T; López-Magano, A; Moya, A; Strutynski, K; Estévez, L; Fernandes, SPS; Misa, I; Sardo, M; Rodriguez-Lorenzo, L; Lebedev, OI; Kolenko, YV; Melle-Franco, M; Mas-Ballesté, R; Salonen, LM
our authors
Clara Alves Ponte
PhD Student
Karol Strutyński
Assistant Researcher
Manuel Melle-Franco
Principal Researcher
Mariana Coutinho Sardo
Assistant ResearcherProjects
Rede Nacional de Ressonância Magnética Nuclear (PTNMR)
Collaboratory for Emerging Technologies, CoLab (EMERGING TECHNOLOGIES)
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)
acknowledgements
This research received funding through the Spanish Ministry of Science and Innovation MCIN/AEI/FEDER (10.13039/501100011033) through the Syrocco project PID2022-137591NA-I00 via Proyectos de Generacion de Conocimiento 2022. CP and KS acknowledge Fundacao para a Cieencia e Tecnologia (FCT) for the Ph.D. scholarship 2021.05983.BD and the grant 2022.07534.CEECIND, respectively. LMS acknowledges financial support through the Ramon y Cajal grant RYC2020-030414-I funded by MICIU/AEI/10.13039/501100011033 and by "ESF Investing in your future". This work is based, in part, upon research conducted under COST Action CA21101 "Confined molecular systems: from a new generation of materials to the stars" (COSY), which is supported by the European Cooperation in Science and Technology. LR-L acknowledges funding from FCT for the Scientific Employment Stimulus Program (2020.04021.CEE-CIND). RM-B acknowledges financial support from the Spanish Government (PID2019-110637RB-I00 and PID2022-141016OB-I00). AM acknowledges the Spanish Government and the Funds Next Generation of the European Union through the grant Maria Zambrano-UAM (CA3/RSUE/2021-00648). The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project N degrees 022161 (cofinanced by FEDER through COMPETE 2020, POCI and PORL, and FCT through PIDDAC). MS also acknowledges FCT for the Assistant Researcher position (2020.00056.CEECIND/CP1589/CT0005 - DOI 10.54499/2020.00056.CEECIND/CP1589/CT0005). KS, MMF, and MS acknowledge support within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 (DOI 10.54499/UIDB/50011/2020), UIDP/50011/2020 (DOI 10.54499/UIDP/50011/2020), and LA/P/0006/2020 (DOI 10.54499/LA/P/0006/2020), financed by national funds through the FCT/MCTES (PIDDAC).