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Controlling the Formation of Two Concomitant Polymorphs in Hg(II) Coordination Polymers
[Image: see text] 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 d...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8965880/ https://www.ncbi.nlm.nih.gov/pubmed/35298147 http://dx.doi.org/10.1021/acs.inorgchem.1c03762 |
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author | Sánchez-Férez, Francisco Solans-Monfort, Xavier Calvet, Teresa Font-Bardia, Mercè Pons, Josefina |
author_facet | Sánchez-Férez, Francisco Solans-Monfort, Xavier Calvet, Teresa Font-Bardia, Mercè Pons, Josefina |
author_sort | Sánchez-Férez, Francisco |
collection | PubMed |
description | [Image: see text] 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. |
format | Online Article Text |
id | pubmed-8965880 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-89658802022-03-30 Controlling the Formation of Two Concomitant Polymorphs in Hg(II) Coordination Polymers Sánchez-Férez, Francisco Solans-Monfort, Xavier Calvet, Teresa Font-Bardia, Mercè Pons, Josefina Inorg Chem [Image: see text] 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. American Chemical Society 2022-03-17 2022-03-28 /pmc/articles/PMC8965880/ /pubmed/35298147 http://dx.doi.org/10.1021/acs.inorgchem.1c03762 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Sánchez-Férez, Francisco Solans-Monfort, Xavier Calvet, Teresa Font-Bardia, Mercè Pons, Josefina Controlling the Formation of Two Concomitant Polymorphs in Hg(II) Coordination Polymers |
title | Controlling the Formation of Two Concomitant Polymorphs
in Hg(II) Coordination Polymers |
title_full | Controlling the Formation of Two Concomitant Polymorphs
in Hg(II) Coordination Polymers |
title_fullStr | Controlling the Formation of Two Concomitant Polymorphs
in Hg(II) Coordination Polymers |
title_full_unstemmed | Controlling the Formation of Two Concomitant Polymorphs
in Hg(II) Coordination Polymers |
title_short | Controlling the Formation of Two Concomitant Polymorphs
in Hg(II) Coordination Polymers |
title_sort | controlling the formation of two concomitant polymorphs
in hg(ii) coordination polymers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8965880/ https://www.ncbi.nlm.nih.gov/pubmed/35298147 http://dx.doi.org/10.1021/acs.inorgchem.1c03762 |
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