Please use this identifier to cite or link to this item:
http://hdl.handle.net/2445/208844
Title: | Controlling the Formation of Two Concomitant Polymorphs in Hg(II)Coordination Polymers |
Author: | Sánchez-Férez, Francisco Solans-Monfort, Xavier Calvet Pallàs, Maria Teresa Font Bardia, Ma. Mercedes Pons, Josefina |
Keywords: | Cristalls Estructura cristal·lina (Sòlids) Cristal·lografia Polímers Crystals Layer structure (Solids) Crystallography Polymers |
Issue Date: | 28-Mar-2022 |
Publisher: | American Chemical Society |
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. |
Note: | Reproducció del document publicat a: https://doi.org/https://doi.org/10.1021/acs.inorgchem.1c03762 |
It is part of: | Inorganic Chemistry, 2022, vol. 61, num.12, p. 4965-4979 |
URI: | http://hdl.handle.net/2445/208844 |
Related resource: | https://doi.org/https://doi.org/10.1021/acs.inorgchem.1c03762 |
ISSN: | 0020-1669 |
Appears in Collections: | Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada) |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
255164.pdf | 11.97 MB | Adobe PDF | View/Open |
This item is licensed under a Creative Commons License