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Polymorphism and solid solutions of trimethylammonium monocarboranes

Grinderslev, Jakob B. ; Skov, Lasse N. ; Sørensen, Daniel R. ; Kantor, Innokenty LU ; Jørgensen, Mads R.V. LU orcid and Jensen, Torben R. (2022) In Dalton Transactions 51(41). p.15806-15815
Abstract

Metal closo-boranes have recently received significant attention as solid-state electrolytes due to their high thermal and electrochemical stability, and the weak interaction between the cat- and anion, facilitating fast ionic conductivity. Here we report a synthesis method for obtaining a novel mixed closo-carborane compound, [NH(CH3)3][(CB8H9)0.26(CB9H10)0.66(CB11H12)0.08]. The crystal structures are investigated for [NH(CH3)3][CB9H10] and... (More)

Metal closo-boranes have recently received significant attention as solid-state electrolytes due to their high thermal and electrochemical stability, and the weak interaction between the cat- and anion, facilitating fast ionic conductivity. Here we report a synthesis method for obtaining a novel mixed closo-carborane compound, [NH(CH3)3][(CB8H9)0.26(CB9H10)0.66(CB11H12)0.08]. The crystal structures are investigated for [NH(CH3)3][CB9H10] and [NH(CH3)3][(CB8H9)0.26(CB9H10)0.66(CB11H12)0.08], revealing that the latter forms a solid solution isostructural to [NH(CH3)3][CB9H10]. The compounds exhibit polymorphism as a function of temperature, and we report the discovery of four polymorphs of [NH(CH3)3][CB9H10] and four isostructural solid solution [NH(CH3)3][(CB8H9)0.26(CB9H10)0.66(CB11H12)0.08], along with a high-temperature decomposition intermediate of the latter. The α-polymorph is an ordered structure, with increasing amounts of disorder for the β- and γ-polymorphs, while the high temperature δ- and ϵ-polymorphs at T > 476 K are fully disordered on both the cation and anion site. These new compounds may be used as precursors for new types of solid-state ionic conductors.

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author
; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
volume
51
issue
41
pages
10 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85140487451
  • pmid:36185033
ISSN
1477-9226
DOI
10.1039/d2dt02513b
language
English
LU publication?
yes
id
5651010e-7d99-45c4-bcf0-3a39f1d556e0
date added to LUP
2023-01-16 12:46:51
date last changed
2025-04-18 07:44:25
@article{5651010e-7d99-45c4-bcf0-3a39f1d556e0,
  abstract     = {{<p>Metal closo-boranes have recently received significant attention as solid-state electrolytes due to their high thermal and electrochemical stability, and the weak interaction between the cat- and anion, facilitating fast ionic conductivity. Here we report a synthesis method for obtaining a novel mixed closo-carborane compound, [NH(CH<sub>3</sub>)<sub>3</sub>][(CB<sub>8</sub>H<sub>9</sub>)<sub>0.26</sub>(CB<sub>9</sub>H<sub>10</sub>)<sub>0.66</sub>(CB<sub>11</sub>H<sub>12</sub>)<sub>0.08</sub>]. The crystal structures are investigated for [NH(CH<sub>3</sub>)<sub>3</sub>][CB<sub>9</sub>H<sub>10</sub>] and [NH(CH<sub>3</sub>)<sub>3</sub>][(CB<sub>8</sub>H<sub>9</sub>)<sub>0.26</sub>(CB<sub>9</sub>H<sub>10</sub>)<sub>0.66</sub>(CB<sub>11</sub>H<sub>12</sub>)<sub>0.08</sub>], revealing that the latter forms a solid solution isostructural to [NH(CH<sub>3</sub>)<sub>3</sub>][CB<sub>9</sub>H<sub>10</sub>]. The compounds exhibit polymorphism as a function of temperature, and we report the discovery of four polymorphs of [NH(CH<sub>3</sub>)<sub>3</sub>][CB<sub>9</sub>H<sub>10</sub>] and four isostructural solid solution [NH(CH<sub>3</sub>)<sub>3</sub>][(CB<sub>8</sub>H<sub>9</sub>)<sub>0.26</sub>(CB<sub>9</sub>H<sub>10</sub>)<sub>0.66</sub>(CB<sub>11</sub>H<sub>12</sub>)<sub>0.08</sub>], along with a high-temperature decomposition intermediate of the latter. The α-polymorph is an ordered structure, with increasing amounts of disorder for the β- and γ-polymorphs, while the high temperature δ- and ϵ-polymorphs at T &gt; 476 K are fully disordered on both the cation and anion site. These new compounds may be used as precursors for new types of solid-state ionic conductors.</p>}},
  author       = {{Grinderslev, Jakob B. and Skov, Lasse N. and Sørensen, Daniel R. and Kantor, Innokenty and Jørgensen, Mads R.V. and Jensen, Torben R.}},
  issn         = {{1477-9226}},
  language     = {{eng}},
  month        = {{09}},
  number       = {{41}},
  pages        = {{15806--15815}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Polymorphism and solid solutions of trimethylammonium monocarboranes}},
  url          = {{http://dx.doi.org/10.1039/d2dt02513b}},
  doi          = {{10.1039/d2dt02513b}},
  volume       = {{51}},
  year         = {{2022}},
}