Document type
ArticleVersion
Accepted versionPublication date
Publication license
Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/208844
Controlling the Formation of Two Concomitant Polymorphs in Hg(II)Coordination Polymers
Journal Title
Director/Tutor
Journal ISSN
Volume Title
Related resource
Abstract
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.
Subject (English)
Citation
Citation
SÁNCHEZ-FÉREZ, Francisco, et al. Controlling the Formation of Two Concomitant Polymorphs in Hg(II)Coordination Polymers. Inorganic Chemistry. 2022. Vol. 61, num. 12, pags. 4965-4979. ISSN 0020-1669. [consulted: 10 of August of 2026]. Available at: https://hdl.handle.net/2445/208844