Polymorphism and solid solutions of trimethylammonium monocarboranes

Jakob B. Grinderslev; Lasse N. Skov; Daniel R. Sørensen; Innokenty Kantor; Mads R.V. Jørgensen; Torben R. Jensen

doi:10.1039/d2dt02513b

Polymorphism and solid solutions of trimethylammonium monocarboranes

Jakob B. Grinderslev
, Lasse N. Skov
, Daniel R. Sørensen
, Innokenty Kantor
, Mads R.V. Jørgensen
, Torben R. Jensen^*

^*Corresponding author for this work

Department of Physics

Research output: Contribution to journal › Journal article › Research › peer-review

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 [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.

Original language	English
Journal	Dalton Transactions
Volume	51
Pages (from-to)	15806–15815
ISSN	1477-9226
DOIs	https://doi.org/10.1039/d2dt02513b
Publication status	Published - 2022

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title = "Polymorphism and solid solutions of trimethylammonium monocarboranes",

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 [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.",

author = "Grinderslev, \{Jakob B.\} and Skov, \{Lasse N.\} and S{\o}rensen, \{Daniel R.\} and Innokenty Kantor and J{\o}rgensen, \{Mads R.V.\} and Jensen, \{Torben R.\}",

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year = "2022",

doi = "10.1039/d2dt02513b",

language = "English",

volume = "51",

pages = "15806–15815",

journal = "Dalton Transactions",

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T1 - Polymorphism and solid solutions of trimethylammonium monocarboranes

AU - Grinderslev, Jakob B.

AU - Skov, Lasse N.

AU - Sørensen, Daniel R.

AU - Kantor, Innokenty

AU - Jørgensen, Mads R.V.

AU - Jensen, Torben R.

PY - 2022

Y1 - 2022

N2 - 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.

AB - 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.

U2 - 10.1039/d2dt02513b

DO - 10.1039/d2dt02513b

M3 - Journal article

C2 - 36185033

AN - SCOPUS:85140487451

SN - 1477-9226

VL - 51

SP - 15806

EP - 15815

JO - Dalton Transactions

JF - Dalton Transactions

ER -

Polymorphism and solid solutions of trimethylammonium monocarboranes

Abstract

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