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

MAX IV Laboratory

Research output: Contribution to journal › Article › 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
Pages (from-to)	15806-15815
Number of pages	10
Journal	Dalton Transactions
Volume	51
Issue number	41
DOIs	https://doi.org/10.1039/d2dt02513b
Publication status	Published - 2022 Sept 27

Subject classification (UKÄ)

Materials Chemistry

Access to Document

10.1039/d2dt02513b

Cite this

@article{5651010e7d9945c4bcf03a39f1d556e0,

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.}",

year = "2022",

month = sep,

day = "27",

doi = "10.1039/d2dt02513b",

language = "English",

volume = "51",

pages = "15806--15815",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "41",

}

TY - JOUR

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 - 2022/9/27

Y1 - 2022/9/27

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 - Article

C2 - 36185033

AN - SCOPUS:85140487451

SN - 1477-9226

VL - 51

SP - 15806

EP - 15815

JO - Dalton Transactions

JF - Dalton Transactions

IS - 41

ER -

Polymorphism and solid solutions of trimethylammonium monocarboranes

Abstract

Subject classification (UKÄ)

Access to Document

Fingerprint

Cite this