Accessing Tetravalent Transition‐Metal Nitridophosphates through High‐Pressure Metathesis

Advancing the attainable composition space of a compound class can lead to fascinating materials. The first tetravalent metal nitridophosphate, namely Hf9−xP24N52−4xO4x (x≈1.84), was prepared by high‐pressure metathesis. The Group 4 nitridophosphates are now an accessible class of compounds. The hig...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-03, Vol.57 (12), p.3192-3195
Main Authors: Kloß, Simon D., Wandelt, Sophia, Weis, Andreas, Schnick, Wolfgang
Format: Article
Language:English
Subjects:
Crystals
Decomposition reactions
Hafnium
high-pressure chemistry
Magnetic properties
Metals
Metathesis
nitrides
Optical measurement
Optical properties
Oxidation
Pressure
Single crystals
solid-state synthesis
Structural analysis
transition metals
Valence
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Summary:Advancing the attainable composition space of a compound class can lead to fascinating materials. The first tetravalent metal nitridophosphate, namely Hf9−xP24N52−4xO4x (x≈1.84), was prepared by high‐pressure metathesis. The Group 4 nitridophosphates are now an accessible class of compounds. The high‐pressure metathesis reaction using a multianvil setup yielded single crystals that were suitable for structure analysis. Magnetic properties of the compound indicate Hf in oxidation state +IV. Optical measurements show a band gap in the UV region. The presented route unlocks the new class of Group 4 nitridophosphates by significantly improving the understanding of this nitride chemistry. Hf9−xP24N52−4xO4x (x≈1.84) is a model system and its preparation is the first step towards a systematic exploration of the transition‐metal nitridophosphates. Working under pressure: A tetravalent transition‐metal nitridophosphate, namely Hf9−xP24N52−4xO4x (x≈1.84), was prepared by high‐pressure metathesis. Its preparation highlights the systematic access to transition‐metal nitridophosphates, which is potentially granted by high‐pressure metathesis.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201712006