Negative and zero linear compressibility in copper dicyanamide and tricyanomethanide

Muzi Chen; Hanna L.B. Boström; Dominik Daisenberger; Nicholas P. Funnell; Christopher J. Ridley; Andrew B. Cairns

doi:10.1039/d5sc04854k

Negative and zero linear compressibility in copper dicyanamide and tricyanomethanide

Muzi Chen
, Hanna L.B. Boström
, Dominik Daisenberger
, Nicholas P. Funnell
, Christopher J. Ridley
, Andrew B. Cairns

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

2 Scopus citations

Abstract

Rutile-structured materials can exhibit negative linear compressibility (NLC) following ferroelastic phase transitions, expanding in one direction under uniform compression. We investigate this phenomenon in structural analogues—transition metal dicyanamides (dca) and tricyanomethanides (tcm) with single and double rutile-like structures, respectively. The pressure-induced structural behaviour of Cu(tcm)₂ and Cu(dca)₂ are studied using high-pressure diffraction. Both systems undergo anisotropic deformation upon compression, with Cu(dca)₂ exhibiting NLC of −6.5(10) TPa⁻¹ along the c-axis, while Cu(tcm)₂ shows zero linear compressibility (ZLC) along the a-axis. This difference is attributed to the single rutile-like network with flexible dca⁻ linkers in Cu(dca)₂, in contrast to the more constrained doubly interpenetrating structure of Cu(tcm)₂ with rigid tcm⁻ linkers. We also study the interplay between structural features and electronic effects arising from the Jahn–Teller distortion in both materials, in controlling their compression behaviour.

Original language	English
Pages (from-to)	3700-3707
Number of pages	8
Journal	Chemical Science
Volume	17
Issue number	7
DOIs	https://doi.org/10.1039/d5sc04854k
State	Published - Feb 18 2026
Externally published	Yes

Funding

We thank the Science and Technology Facilities Council ISIS Neutron and Muon Source (STFC ISIS Facility) (data DOI:https://www.doi.org/10.5286/ISIS.E.RB2010698) and the Diamond Light Source (proposal number CY29285) for the provision of beamtime. We thank the European Synchrotron Radiation Facility (ESRF) for providing beamtime through ABC's postdoctoral fellowship. HLBB acknowledges financial support from the Swedish Research Council (VR, grant number 2022-02984) and the Wallenberg Initiative Materials Science for Sustainability (WISE), funded by the Knut and Alice Wallenberg Foundation.

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@article{103b7cc2220e4b78981ba65853b56ac0,

title = "Negative and zero linear compressibility in copper dicyanamide and tricyanomethanide",

abstract = "Rutile-structured materials can exhibit negative linear compressibility (NLC) following ferroelastic phase transitions, expanding in one direction under uniform compression. We investigate this phenomenon in structural analogues{\textemdash}transition metal dicyanamides (dca) and tricyanomethanides (tcm) with single and double rutile-like structures, respectively. The pressure-induced structural behaviour of Cu(tcm)2 and Cu(dca)2 are studied using high-pressure diffraction. Both systems undergo anisotropic deformation upon compression, with Cu(dca)2 exhibiting NLC of −6.5(10) TPa−1 along the c-axis, while Cu(tcm)2 shows zero linear compressibility (ZLC) along the a-axis. This difference is attributed to the single rutile-like network with flexible dca− linkers in Cu(dca)2, in contrast to the more constrained doubly interpenetrating structure of Cu(tcm)2 with rigid tcm− linkers. We also study the interplay between structural features and electronic effects arising from the Jahn{\textendash}Teller distortion in both materials, in controlling their compression behaviour.",

author = "Muzi Chen and Bostr{\"o}m, \{Hanna L.B.\} and Dominik Daisenberger and Funnell, \{Nicholas P.\} and Ridley, \{Christopher J.\} and Cairns, \{Andrew B.\}",

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month = feb,

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doi = "10.1039/d5sc04854k",

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TY - JOUR

T1 - Negative and zero linear compressibility in copper dicyanamide and tricyanomethanide

AU - Chen, Muzi

AU - Boström, Hanna L.B.

AU - Daisenberger, Dominik

AU - Funnell, Nicholas P.

AU - Ridley, Christopher J.

AU - Cairns, Andrew B.

PY - 2026/2/18

Y1 - 2026/2/18

N2 - Rutile-structured materials can exhibit negative linear compressibility (NLC) following ferroelastic phase transitions, expanding in one direction under uniform compression. We investigate this phenomenon in structural analogues—transition metal dicyanamides (dca) and tricyanomethanides (tcm) with single and double rutile-like structures, respectively. The pressure-induced structural behaviour of Cu(tcm)2 and Cu(dca)2 are studied using high-pressure diffraction. Both systems undergo anisotropic deformation upon compression, with Cu(dca)2 exhibiting NLC of −6.5(10) TPa−1 along the c-axis, while Cu(tcm)2 shows zero linear compressibility (ZLC) along the a-axis. This difference is attributed to the single rutile-like network with flexible dca− linkers in Cu(dca)2, in contrast to the more constrained doubly interpenetrating structure of Cu(tcm)2 with rigid tcm− linkers. We also study the interplay between structural features and electronic effects arising from the Jahn–Teller distortion in both materials, in controlling their compression behaviour.

AB - Rutile-structured materials can exhibit negative linear compressibility (NLC) following ferroelastic phase transitions, expanding in one direction under uniform compression. We investigate this phenomenon in structural analogues—transition metal dicyanamides (dca) and tricyanomethanides (tcm) with single and double rutile-like structures, respectively. The pressure-induced structural behaviour of Cu(tcm)2 and Cu(dca)2 are studied using high-pressure diffraction. Both systems undergo anisotropic deformation upon compression, with Cu(dca)2 exhibiting NLC of −6.5(10) TPa−1 along the c-axis, while Cu(tcm)2 shows zero linear compressibility (ZLC) along the a-axis. This difference is attributed to the single rutile-like network with flexible dca− linkers in Cu(dca)2, in contrast to the more constrained doubly interpenetrating structure of Cu(tcm)2 with rigid tcm− linkers. We also study the interplay between structural features and electronic effects arising from the Jahn–Teller distortion in both materials, in controlling their compression behaviour.

UR - https://www.scopus.com/pages/publications/105026402419

U2 - 10.1039/d5sc04854k

DO - 10.1039/d5sc04854k

M3 - Article

AN - SCOPUS:105026402419

SN - 2041-6520

VL - 17

SP - 3700

EP - 3707

JO - Chemical Science

JF - Chemical Science

IS - 7

ER -

Negative and zero linear compressibility in copper dicyanamide and tricyanomethanide

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