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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/207324
Pyridine-driven assembly of Zn(II) and Cd(II) complexes with 2-furoic acid. The role of water in a structural transformation
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Understanding the factors governing the self-assembly of organic ligands with metal ions is essential to engineering target molecular arrangements with the desired properties. Indeed, small modifications of the synthetic conditions lead to the obtention of different complexes, varying from discrete monomers to coordination polymers (CPs). Based on the potential coordinating ability of 2-furoic acid (2-FA), we prepared five Zn(II) and Cd(II) complexes to study the behavior of the furane O atom and the competitiveness of the M-O bond formation in methanol (MeOH). Reactions between M(OAc)(2 center dot)2H(2)O (M = Zn(II), Cd(II)), 2-FA, and two p-substituted pyridine ligands (isonicotinamide (Isn) and 4-acetylpyridine (4-Acpy)) in MeOH yielded the two dimers [Zn(mu-2-FA)(2-FA)(Isn)(2)](2) (1) and [Cd(mu-2-FA)(2-FA)(Isn)(2)](2) (2), the dimeric paddle-wheel [Zn(mu-2-FA)(2)(4-Acpy)](2) (3), and the monomer [Cd(2-FA)(2)(4-Acpy)(2)(OH2)] (4). Their crystal structures have been studied, observing diverse coordination numbers between five and seven and diverse coordination modes of the carboxylate groups. Interestingly, the recrystallization of 4 in acetonitrile (ACN) resulted in a dissolution-recrystallization structural transformation (DRST), leading to an intricate coordination polymer (CP) with the formula {[Cd(mu-2-FA)(2-FA)(OH2)(2)](n)[Cd(mu-2-FA)(2-FA)(4-Acpy)(OH2)](n)} (5) exhibiting coordination of the furane O atom. Within this collection of arrangements, 2-FA displayed a great diversity of coordination modes that were combined and interchanged in the DRST process. Their photophysical properties in solution have been analyzed and their quantum yields calculated. Likewise, further insight into the DRST process was obtained from fluorescence measurements. From these results, a pathway for the structural transformation highlighting the crucial role of solvents has been proposed.
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EJARQUE, Daniel, et al. Pyridine-driven assembly of Zn(II) and Cd(II) complexes with 2-furoic acid. The role of water in a structural transformation. Crystengcomm. 2023. Vol. 25, num. 18, pags. 2739-2754. ISSN 1466-8033. [consulted: 14 of June of 2026]. Available at: https://hdl.handle.net/2445/207324