Pyridine-driven assembly of Zn(II) and Cd(II) complexes with 2-furoic acid. The role of water in a structural transformation
Ejarque, Daniel (Universitat Autònoma de Barcelona. Departament de Química)
Sánchez Férez, Francisco (Universitat Autònoma de Barcelona. Departament de Química)
Félez-Guerrero, Núria (Universitat Autònoma de Barcelona. Departament de Química)
Calvet, Teresa (Universitat de Barcelona. Departament de Mineralogia, Petrologia i Geologia Aplicada)
Font-Bardia, Mercè (Universitat de Barcelona. Centres Científics i Tecnològics)
Pons Picart, Josefina (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2023
Resum:	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)2·2H2O (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(μ-2-FA)(2-FA)(Isn)2]2 (1) and [Cd(μ-2-FA)(2-FA)(Isn)2]2 (2), the dimeric paddle-wheel [Zn(μ-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(μ-2-FA)(2-FA)(OH2)2]n[Cd(μ-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.
Ajuts:	Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1687 "la Caixa" Foundation CB615921 "la Caixa" Foundation CB616406
Nota:	Altres ajuts: acords transformatius de la UAB
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	CrystEngComm, Vol. 25, Issue 18 (May 2023) , p. 2739-2754, ISSN 1466-8033

DOI: 10.1039/D3CE00104K

16 p, 2.2 MB

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