Polymorphs and solid solutions: materials with new luminescent properties obtained through mechanochemical transformation of dicyanoaurate(i) salts

Jogirdas Vainauskas; Filip Topić; Mihails Arhangelskis; Hatem M. Titi; Tomislav Friščić

doi:10.1039/d2fd00134a

Polymorphs and solid solutions: materials with new luminescent properties obtained through mechanochemical transformation of dicyanoaurate(i) salts

Jogirdas Vainauskas
, Filip Topić
, Mihails Arhangelskis
, Hatem M. Titi
, Tomislav Friščić^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

We report the use of mechano- and thermochemical methods to create new solid-state luminescent materials from well-known inorganic salts, potassium dicyanoaurate(i) KAu(CN)₂, and potassium dicyanocuprate(i) KCu(CN)₂. In particular, manual grinding or ball milling of commercial samples of KAu(CN)₂ led to the formation of a novel polymorph of the salt, herein termed m-KAu(CN)₂, evident by a significant change in color of the fluorescence emission of the solid material from orange to violet. The formation of m-KAu(CN)₂ is reversible upon addition of small amounts of solvents, and powder X-ray diffraction analysis indicates that the structure of m-KAu(CN)₂ might be related to that of pristine KAu(CN)₂ through a change in ordering of Au(CN)₂⁻ ions in a layered structure. Thermal treatment of KAu(CN)₂ led to the discovery of another polymorph of this well-known salt, herein termed t-KAu(CN)₂, making KAu(CN)₂ a rare example of a system in which thermochemical and mechanochemical treatments lead to the formation of different, in each case previously not reported, polymorphic forms. The thermally-induced transformation from KAu(CN)₂ to t-KAu(CN)₂ takes place around 250 °C and proceeds in a crystal-to-crystal fashion, which enabled the preliminary structural characterisation through single crystal X-ray diffraction, revealing the retention of the layered structure and a change in ordering of Au(CN)₂⁻ ions.

Original language	English
Pages (from-to)	425-447
Number of pages	23
Journal	Faraday Discussions
Volume	241
Early online date	25 Jul 2022
DOIs	https://doi.org/10.1039/d2fd00134a
Publication status	Published - 1 Jan 2023

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Publisher Copyright:
© 2023 The Royal Society of Chemistry.

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1039/d2fd00134a

Cite this

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title = "Polymorphs and solid solutions: materials with new luminescent properties obtained through mechanochemical transformation of dicyanoaurate(i) salts",

abstract = "We report the use of mechano- and thermochemical methods to create new solid-state luminescent materials from well-known inorganic salts, potassium dicyanoaurate(i) KAu(CN)2, and potassium dicyanocuprate(i) KCu(CN)2. In particular, manual grinding or ball milling of commercial samples of KAu(CN)2 led to the formation of a novel polymorph of the salt, herein termed m-KAu(CN)2, evident by a significant change in color of the fluorescence emission of the solid material from orange to violet. The formation of m-KAu(CN)2 is reversible upon addition of small amounts of solvents, and powder X-ray diffraction analysis indicates that the structure of m-KAu(CN)2 might be related to that of pristine KAu(CN)2 through a change in ordering of Au(CN)2− ions in a layered structure. Thermal treatment of KAu(CN)2 led to the discovery of another polymorph of this well-known salt, herein termed t-KAu(CN)2, making KAu(CN)2 a rare example of a system in which thermochemical and mechanochemical treatments lead to the formation of different, in each case previously not reported, polymorphic forms. The thermally-induced transformation from KAu(CN)2 to t-KAu(CN)2 takes place around 250 °C and proceeds in a crystal-to-crystal fashion, which enabled the preliminary structural characterisation through single crystal X-ray diffraction, revealing the retention of the layered structure and a change in ordering of Au(CN)2− ions.",

author = "Jogirdas Vainauskas and Filip Topi{\'c} and Mihails Arhangelskis and Titi, \{Hatem M.\} and Tomislav Fri{\v s}{\v c}i{\'c}",

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T2 - materials with new luminescent properties obtained through mechanochemical transformation of dicyanoaurate(i) salts

AU - Vainauskas, Jogirdas

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AU - Titi, Hatem M.

AU - Friščić, Tomislav

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N2 - We report the use of mechano- and thermochemical methods to create new solid-state luminescent materials from well-known inorganic salts, potassium dicyanoaurate(i) KAu(CN)2, and potassium dicyanocuprate(i) KCu(CN)2. In particular, manual grinding or ball milling of commercial samples of KAu(CN)2 led to the formation of a novel polymorph of the salt, herein termed m-KAu(CN)2, evident by a significant change in color of the fluorescence emission of the solid material from orange to violet. The formation of m-KAu(CN)2 is reversible upon addition of small amounts of solvents, and powder X-ray diffraction analysis indicates that the structure of m-KAu(CN)2 might be related to that of pristine KAu(CN)2 through a change in ordering of Au(CN)2− ions in a layered structure. Thermal treatment of KAu(CN)2 led to the discovery of another polymorph of this well-known salt, herein termed t-KAu(CN)2, making KAu(CN)2 a rare example of a system in which thermochemical and mechanochemical treatments lead to the formation of different, in each case previously not reported, polymorphic forms. The thermally-induced transformation from KAu(CN)2 to t-KAu(CN)2 takes place around 250 °C and proceeds in a crystal-to-crystal fashion, which enabled the preliminary structural characterisation through single crystal X-ray diffraction, revealing the retention of the layered structure and a change in ordering of Au(CN)2− ions.

AB - We report the use of mechano- and thermochemical methods to create new solid-state luminescent materials from well-known inorganic salts, potassium dicyanoaurate(i) KAu(CN)2, and potassium dicyanocuprate(i) KCu(CN)2. In particular, manual grinding or ball milling of commercial samples of KAu(CN)2 led to the formation of a novel polymorph of the salt, herein termed m-KAu(CN)2, evident by a significant change in color of the fluorescence emission of the solid material from orange to violet. The formation of m-KAu(CN)2 is reversible upon addition of small amounts of solvents, and powder X-ray diffraction analysis indicates that the structure of m-KAu(CN)2 might be related to that of pristine KAu(CN)2 through a change in ordering of Au(CN)2− ions in a layered structure. Thermal treatment of KAu(CN)2 led to the discovery of another polymorph of this well-known salt, herein termed t-KAu(CN)2, making KAu(CN)2 a rare example of a system in which thermochemical and mechanochemical treatments lead to the formation of different, in each case previously not reported, polymorphic forms. The thermally-induced transformation from KAu(CN)2 to t-KAu(CN)2 takes place around 250 °C and proceeds in a crystal-to-crystal fashion, which enabled the preliminary structural characterisation through single crystal X-ray diffraction, revealing the retention of the layered structure and a change in ordering of Au(CN)2− ions.

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ER -

Polymorphs and solid solutions: materials with new luminescent properties obtained through mechanochemical transformation of dicyanoaurate(i) salts

Abstract

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