Controlling the formation of two concomitant polymorphs in Hg(II) coordination polymers
Sánchez Férez, Francisco (Universitat Autònoma de Barcelona. Departament de Química)
Solans Monfort, Xavier (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:	2022
Resum:	Controlling the formation of the desired product in the appropriate crystalline form is the fundamental breakthrough of crystal engineering. On that basis, the preferential formation between polymorphic forms, which are referred to as different assemblies achieved by changing the disposition or arrangement of the forming units within the crystalline structure, is one of the most challenging topics still to be understood. Herein, we have observed the formation of two concomitant polymorphs with general formula {[Hg(Pip)2(4,4'-bipy)]·DMF}n (P1A, P1B; Pip = piperonylic acid; 4,4'-bipy = 4,4'-bipyridine). Besides, [Hg(Pip)2(4,4'-bipy)]n (2) has been achieved during the attempts to isolate these polymorphs. The selective synthesis of P1A and P1B has been successfully achieved by changing the synthetic conditions. The formation of each polymorphic form has been ensured by unit cell measurements and decomposition temperature. The elucidation of their crystal structure revealed P1A and P1B as polymorphs, which originates from the Hg(II) cores and intermolecular associations, especially pinpointed by Hg···π and π···π interactions. Density functional theory (DFT) calculations suggest that P1B, which shows Hg(II) geometries that are further from ideality, is more stable than P1A by 13 kJ·mol-1 per [Hg(Pip)2(4,4'-bipy)]·DMF formula unit, and this larger stability of P1B arises mainly from metal···π and π···π interactions between chains. As a result, these structural modifications lead to significant variations of their solid-state photoluminescence.
Ajuts:	Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1687 Agencia Estatal de Investigación PID2020-112715GB-I00
Nota:	Altres ajuts: acords transformatius de la UAB
Nota:	Altres ajuts: J.P. acknowledges financial support from the CB615921 project, the CB616406 project from "Fundació La Caixa"
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
Matèria:	Crystals ; Crystal structure ; Mercury ; Mathematical methods ; Molecular interactions
Publicat a:	Inorganic chemistry, (March 2022) , ISSN 1520-510X

DOI: 10.1021/acs.inorgchem.1c03762
PMID: 35298147

15 p, 11.8 MB

Supporting information 15 p, 1.9 MB

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