Phase transition originating from order-disorder transformations of carboxy oxygen atoms coupled with dynamic proton motions in [PhCH2 NH(CH3)2]2 C2O4⋅H2 C2O4

Yuanyuan Tang; Chengmin Ji; Zhihua Sun; Shuquan Zhang; Tianliang Chen; Junhua Luo

doi:10.1002/asia.201402132

Phase transition originating from order-disorder transformations of carboxy oxygen atoms coupled with dynamic proton motions in [PhCH2 NH(CH3)2]2 C2O4⋅H2 C2O4

Chem Asian J. 2014 Jul;9(7):1771-6. doi: 10.1002/asia.201402132. Epub 2014 Jun 4.

Authors

Yuanyuan Tang¹, Chengmin Ji, Zhihua Sun, Shuquan Zhang, Tianliang Chen, Junhua Luo

Affiliation

¹ College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350108 (China); Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China).

PMID: 24895117
DOI: 10.1002/asia.201402132

Abstract

A new molecular phase transition material, [PhCH(2) NH(CH(3))(2)](2) C(2)O(4)⋅H(2)C(2)O(4), which undergoes a reversible phase transition at 151.6 K, has been successfully synthesized. Differential scanning calorimetry (DSC), specific heat capacity, and dielectric measurements confirm its reversible phase transition with a large thermal hysteresis of 15.1 K, demonstrating that the phase transition is typical first order. Variable-temperature single-crystal X-ray diffraction analyses reveal that the order-disorder transformations of carboxy oxygen atoms induce the structural phase transition. A slight reorientation of the oxalic acid unit is discovered to accompany the ordering of carboxy oxygen atoms at low temperature. The DSC measurement result of the deuterated analog is different to that of 1, indicating that proton dynamic motions in hydrogen bonds also contribute to the phase transition.

Keywords: crystal growth; isotope effects; order-disorder; oxalic acid; phase transitions.