Cargando…

Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co)

Increased synthetic control in borosulfate chemistry leads to the access of various new compounds. Herein, the polymorphism of phyllosilicate‐analogous borosulfates is unraveled by adjusting the oleum (65 % SO(3)) content. The new polymorphs β‐Mg[B(2)(SO(4))(4)] and α‐Co[B(2)(SO(4))(4)] both consist...

Descripción completa

Detalles Bibliográficos
Autores principales: Netzsch, Philip, Pielnhofer, Florian, Glaum, Robert, Höppe, Henning A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7756226/
https://www.ncbi.nlm.nih.gov/pubmed/32744744
http://dx.doi.org/10.1002/chem.202003214
_version_ 1783626494628593664
author Netzsch, Philip
Pielnhofer, Florian
Glaum, Robert
Höppe, Henning A.
author_facet Netzsch, Philip
Pielnhofer, Florian
Glaum, Robert
Höppe, Henning A.
author_sort Netzsch, Philip
collection PubMed
description Increased synthetic control in borosulfate chemistry leads to the access of various new compounds. Herein, the polymorphism of phyllosilicate‐analogous borosulfates is unraveled by adjusting the oleum (65 % SO(3)) content. The new polymorphs β‐Mg[B(2)(SO(4))(4)] and α‐Co[B(2)(SO(4))(4)] both consist of similar layers of alternating borate and sulfate tetrahedra, but differ in the position of octahedrally coordinated cations. The α‐modification comprises cations between the layers, whereas in the β‐modification cations are embedded within the layers. With this new synthetic approach, phase‐pure compounds of the respective polymorphs α‐Mg[B(2)(SO(4))(4)] and β‐Co[B(2)(SO(4))(4)] were also achieved. Tanabe–Sugano analysis of the Co(2+) polymorphs reveal weak ligand field splitting and give insights into the coordination behavior of the two‐dimensional borosulfate anions for the first time. DFT calculations confirmed previous in silico experiments and enabled an assignment of the polymorphs by comparing the total electronic energies. The compounds are characterized by single‐crystal XRD, PXRD, FTIR, and UV/Vis/NIR spectroscopy, thermogravimetric analysis (TGA), and density functional theory (DFT) calculations.
format Online
Article
Text
id pubmed-7756226
institution National Center for Biotechnology Information
language English
publishDate 2020
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-77562262020-12-28 Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co) Netzsch, Philip Pielnhofer, Florian Glaum, Robert Höppe, Henning A. Chemistry Full Papers Increased synthetic control in borosulfate chemistry leads to the access of various new compounds. Herein, the polymorphism of phyllosilicate‐analogous borosulfates is unraveled by adjusting the oleum (65 % SO(3)) content. The new polymorphs β‐Mg[B(2)(SO(4))(4)] and α‐Co[B(2)(SO(4))(4)] both consist of similar layers of alternating borate and sulfate tetrahedra, but differ in the position of octahedrally coordinated cations. The α‐modification comprises cations between the layers, whereas in the β‐modification cations are embedded within the layers. With this new synthetic approach, phase‐pure compounds of the respective polymorphs α‐Mg[B(2)(SO(4))(4)] and β‐Co[B(2)(SO(4))(4)] were also achieved. Tanabe–Sugano analysis of the Co(2+) polymorphs reveal weak ligand field splitting and give insights into the coordination behavior of the two‐dimensional borosulfate anions for the first time. DFT calculations confirmed previous in silico experiments and enabled an assignment of the polymorphs by comparing the total electronic energies. The compounds are characterized by single‐crystal XRD, PXRD, FTIR, and UV/Vis/NIR spectroscopy, thermogravimetric analysis (TGA), and density functional theory (DFT) calculations. John Wiley and Sons Inc. 2020-10-07 2020-11-17 /pmc/articles/PMC7756226/ /pubmed/32744744 http://dx.doi.org/10.1002/chem.202003214 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Full Papers
Netzsch, Philip
Pielnhofer, Florian
Glaum, Robert
Höppe, Henning A.
Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co)
title Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co)
title_full Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co)
title_fullStr Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co)
title_full_unstemmed Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co)
title_short Synthesis‐Controlled Polymorphism and Optical Properties of Phyllosilicate‐Analogous Borosulfates M[B(2)(SO(4))(4)] (M=Mg, Co)
title_sort synthesis‐controlled polymorphism and optical properties of phyllosilicate‐analogous borosulfates m[b(2)(so(4))(4)] (m=mg, co)
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7756226/
https://www.ncbi.nlm.nih.gov/pubmed/32744744
http://dx.doi.org/10.1002/chem.202003214
work_keys_str_mv AT netzschphilip synthesiscontrolledpolymorphismandopticalpropertiesofphyllosilicateanalogousborosulfatesmb2so44mmgco
AT pielnhoferflorian synthesiscontrolledpolymorphismandopticalpropertiesofphyllosilicateanalogousborosulfatesmb2so44mmgco
AT glaumrobert synthesiscontrolledpolymorphismandopticalpropertiesofphyllosilicateanalogousborosulfatesmb2so44mmgco
AT hoppehenninga synthesiscontrolledpolymorphismandopticalpropertiesofphyllosilicateanalogousborosulfatesmb2so44mmgco