Water as a Modifier in a Hybrid Coordination Network Glass

Søren Strandskov Sørensen, Xiangting Ren, Tao Du, Ayoub Traverson, Shibo Xi, Lars Rosgaard Jensen, Mathieu Bauchy, Satoshi Horike, John Wang, Morten Mattrup Smedskjær*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

3 Citations (Scopus)
36 Downloads (Pure)

Abstract

Chemical diversification of hybrid organic–inorganic glasses remains limited, especially compared to traditional oxide glasses, for which property tuning is possible through addition of weakly bonded modifier cations. In this work, it is shown that water can depolymerize polyhedra with labile metal–ligand bonds in a cobalt-based coordination network, yielding a series of nonstoichiometric glasses. Calorimetric, spectroscopic, and simulation studies demonstrate that the added water molecules promote the breakage of network bonds and coordination number changes, leading to lower melting and glass transition temperatures. These structural changes modify the physical and chemical properties of the melt-quenched glass, with strong parallels to the “modifier” concept in oxides. It is shown that this approach also applies to other transition metal-based coordination networks, and it will thus enable diversification of hybrid glass chemistry, including nonstoichiometric glass compositions, tuning of properties, and a significant rise in the number of glass-forming hybrid systems by allowing them to melt before thermal decomposition.

Original languageEnglish
Article number2205988
JournalSmall
Volume19
Issue number14
ISSN1613-6829
DOIs
Publication statusPublished - 5 Apr 2023

Keywords

  • coordination networks
  • glass modifiers
  • hybrid glasses
  • melting
  • water

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