Hydrogen-bonded displacive-type ferroelastic phase transition in a new entangled supramolecular compound - Details

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Abstract：

The　framework　entanglements　show　structural　transitions　by　the　removal　and　incorporation　of　guest　molecules,　but　rarely　generate　phase　transitions　by　themselves.　In　this　study,　we　report　a　new　entangled　hydrogen-bonded　supramolecular　compound,　[(n-C4H9)2NH2]2H2C4O4·H4C4O4　(1,　H4C4O4　=　fumaric　acid),　which　undergoes　a　reversible　ferroelastic　phase　transition　with　the　Aizu　notation　of　2/mF1?.　Differential　scanning　calorimetry　and　specific　heat　measurements　confirm　its　typical　second-order　phase　transition　at　around　228.8　K　(Tc),　while　the　results　of　the　deuterated　analogue　(2)　are　different　with　those　of　1,　indicating　that　proton　dynamic　motions　in　hydrogen　bonds　contribute　to　the　phase　transition.　Variable-temperature　single-crystal　X-ray　diffraction　analyses　reveal　that　the　cooperative　displacements　of　hydrogen　bonds　induce　the　structural　phase　transition,　which　arise　from　the　twisting　motions　of　the　fumaric　acid　molecules.　Simultaneously,　two　types　of　independent　hydrogen　bonding　layers　in　the　entanglement　are　altered　in　response　to　the　transformation　of　hydrogen　bonds　aggregates　at　the　low　temperature　phase,　causing　the　symmetry　breaking.　These　findings　will　open　up　a　new　avenue　for　the　design　of　ferroic　materials　with　an　entangled　framework.　©　2014　American　Chemical　Society.

Keyword：

Complexation Differential scanning calorimetry Hydrogen bonds Molecules Single crystals Specific heat Supramolecular chemistry Temperature Thermal variables measurement X ray diffraction analysis

Community：

[ 1 ] [Tang, Yuanyuan]Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 2 ] [Tang, Yuanyuan]College of Chemistry, Fuzhou University, Fuzhou; 350116, China
[ 3 ] [Tang, Yuanyuan]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 4 ] [Sun, Zhihua]Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 5 ] [Sun, Zhihua]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 6 ] [Sun, Zhihua]State Key Laboratory of Crystal Material, Shandong University, Jinan; 250100, China
[ 7 ] [Ji, Chengmin]Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 8 ] [Li, Lina]Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 9 ] [Li, Lina]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 10 ] [Zhang, Shuquan]Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 11 ] [Zhang, Shuquan]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 12 ] [Chen, Tianliang]Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 13 ] [Chen, Tianliang]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 14 ] [Luo, Junhua]Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China
[ 15 ] [Luo, Junhua]College of Chemistry, Fuzhou University, Fuzhou; 350116, China
[ 16 ] [Luo, Junhua]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou; 350002, China

Reprint 's Address：

[luo, junhua]college of chemistry, fuzhou university, fuzhou; 350116, china;;[luo, junhua]key laboratory of optoelectronic materials chemistry and physics, fujian institute of research on the structure of matter, chinese academy of sciences, fuzhou; 350002, china;;[luo, junhua]state key laboratory of structural chemistry, fujian institute of research on the structure of matter, chinese academy of sciences, fuzhou; 350002, china

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Source ：

Crystal Growth and Design

ISSN： 1528-7483

Year： 2015

Issue： 1

Volume： 15

Page： 457-464

4 . 4 2 5

JCR@2015

3 . 2 0 0

JCR@2023

ESI HC Threshold：265

JCR Journal Grade：1

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ESI Highly Cited Papers on the List： 0 Unfold All

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30 Days PV： 0

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