Hydrogen-bonded nickel(II)-organosulfonate framework: Thermal expansion behavior, proton conduction, and magnetic properties

Zhang，Yang Lu1; Shi，Le2; Liu，Genyan3; Yang，Jiong4; Shao，Dong1,5

2023-11-15

10.1016/j.molstruc.2023.136131

Journal of Molecular Structure   Impact Factor & Quartile

0022-2860

1872-8014

Metalo Hydrogen-bonded organic frameworks are emerging supramolecular platforms for designing functional molecular materials. Herein, we reported the supramolecular structure, thermal, magnetic, and proton conduction properties of a hydrogen-bonded nickel(II)-organosulfonate framework, [Ni(HO)][NPS] (NiHOF, HNPS = naphthalene-2-sulphonic acid). Single-crystal X-ray diffraction studies reveal a two-dimensional hydrogen-bonded network sustained by multiple and charge-assisted O–H···O H bonds between hexaaquanickel(II) cations and organosulfonate anions. Additionally, continuous ca. 0.47 × 0.70 nm windows were formed within the framework. The thermal stability of the NiHOF was confirmed by thermal gravimetric analysis and variable temperature single-crystal and powder X-ray diffraction patterns. N sorption isotherms suggest an ultramicroporous supramolecular framework of NiHOF with permanent porosity. The anisotropic positive thermal expansion behavior of NiHOF was evidenced by the dynamic crystallography experiments. Magnetic measurements indicate easy-axis magnetic anisotropy (D = -10.5 cm) of the NiHOF while no slow magnetic relaxation behavior. Electrochemical impedance spectroscopy indicates the temperature and humidity dependence of conductivities of NiHOF. At 50 °C and 70% relative humidity, the conductivity is 1.13 × 10 S·cm, revealing a supramolecular proton conductor of NiHOF. This work provides a potential way for designing novel thermal, magnetic, and electrical molecular materials through the supramolecular assembly of inorganic and organosulfonate synthons.

Hydrogen-bonded framework Magnetic property Ni(II) complex Proton conduction Thermal expansion

SCI

English

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Chutian Scholars Program of Hubei Province, HuanggangNormal University["2042021033","202210204"] ; Young Talents Project of the Department of Education of Hubei Province[Q20222904] ; Open Foundation of Hubei Key Laboratory of Novel Reactor and Green Chemical Technology[NRGC202210] ; Open Foundation of State Key Laboratory of Coordination Chemistry[SKLCC2208]

Chemistry

Chemistry, Physical

WOS:001046877200001

ELSEVIER

CHEMISTRY

2-s2.0-85164672003

Scopus

1.Hubei Key Laboratory of Processing and Application of Catalytic Materials,College of Chemistry and Chemical Engineering,Huanggang Normal University,Huanggang,438000,China
2.State Key Laboratory of Chemical Engineering,Stoddart Institute of Molecular Science,Department of Chemistry,Zhejiang University,Hangzhou,310027,China
3.Hubei Key Laboratory of Novel Reactor and Green Chemical Technology,Wuhan Institute of Technology,Wuhan,430205,China
4.Department of Chemistry,Southern University of Science and Technology (SUSTech),Shenzhen,518055,China
5.State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing,210023,China

Zhang，Yang Lu,Shi，Le,Liu，Genyan,et al. Hydrogen-bonded nickel(II)-organosulfonate framework: Thermal expansion behavior, proton conduction, and magnetic properties[J]. Journal of Molecular Structure,2023,1292.

Zhang，Yang Lu,Shi，Le,Liu，Genyan,Yang，Jiong,&Shao，Dong.(2023).Hydrogen-bonded nickel(II)-organosulfonate framework: Thermal expansion behavior, proton conduction, and magnetic properties.Journal of Molecular Structure,1292.

Zhang，Yang Lu,et al."Hydrogen-bonded nickel(II)-organosulfonate framework: Thermal expansion behavior, proton conduction, and magnetic properties".Journal of Molecular Structure 1292(2023).