A semiconducting layered metal-organic framework magnet

Chongqing Yang; Renhao Dong; Mao Wang; Petko St Petkov; Zhitao Zhang; Mingchao Wang; Peng Han; Marco Ballabio; Sascha A Bräuninger; Zhongquan Liao; Jichao Zhang; Friedrich Schwotzer; Ehrenfried Zschech; Hans-Henning Klauss; Enrique Cánovas; Stefan Kaskel; Mischa Bonn; Shengqiang Zhou; Thomas Heine; Xinliang Feng

doi:10.1038/s41467-019-11267-w

A semiconducting layered metal-organic framework magnet

Nat Commun. 2019 Jul 22;10(1):3260. doi: 10.1038/s41467-019-11267-w.

Authors

Chongqing Yang^{1

2}, Renhao Dong³, Mao Wang⁴, Petko St Petkov⁵, Zhitao Zhang⁴, Mingchao Wang¹, Peng Han⁶, Marco Ballabio⁶, Sascha A Bräuninger⁷, Zhongquan Liao⁸, Jichao Zhang⁹, Friedrich Schwotzer¹, Ehrenfried Zschech⁸, Hans-Henning Klauss⁷, Enrique Cánovas^{6

10}, Stefan Kaskel¹, Mischa Bonn⁶, Shengqiang Zhou⁴, Thomas Heine^{1

4

11}, Xinliang Feng^{12

13}

Affiliations

¹ Center for Advancing Electronics Dresden (cfaed) & Department of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01062, Dresden, Germany.
² School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Dongchuan Road 800, 200240, Shanghai, China.
³ Center for Advancing Electronics Dresden (cfaed) & Department of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01062, Dresden, Germany. renhao.dong@tu-dresden.de.
⁴ Helmholtz-Zentrum Dresden-Rossendorf, Institute of Ion Beam Physics and Materials Research, Bautzner Landstr. 400, 01328, Dresden, Germany.
⁵ University of Sofia, Faculty of Chemistry and Pharmacy, J. Bourchier blvd. 1, 1164, Sofia, Bulgaria.
⁶ Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany.
⁷ Institut für Festkörper und Materialphysik, Technische Universität Dresden, 01062, Dresden, Germany.
⁸ Fraunhofer Institute for Ceramic Technologies and Systems (IKTS), 01109, Dresden, Germany.
⁹ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, No.239 Zhangheng Road, Shanghai, 201204, China.
¹⁰ Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanociencia), Faraday 9, 28049, Madrid, Spain.
¹¹ Wilhelm-Ostwald-Institute of Physical and Theoretical Chemistry, Leipzig University, Linnéstr. 2, 04103, Leipzig, Germany.
¹² Center for Advancing Electronics Dresden (cfaed) & Department of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01062, Dresden, Germany. xinliang.feng@tu-dresden.de.
¹³ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Dongchuan Road 800, 200240, Shanghai, China. xinliang.feng@tu-dresden.de.

Abstract

The realization of ferromagnetism in semiconductors is an attractive avenue for the development of spintronic applications. Here, we report a semiconducting layered metal-organic framework (MOF), namely K₃Fe₂[(2,3,9,10,16,17,23,24-octahydroxy phthalocyaninato)Fe] (K₃Fe₂[PcFe-O₈]) with spontaneous magnetization. This layered MOF features in-plane full π-d conjugation and exhibits semiconducting behavior with a room temperature carrier mobility of 15 ± 2 cm² V^-1 s^-1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and ⁵⁷Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K₃Fe₂[PcFe-O₈] arising from the magnetic coupling between iron centers via delocalized π electrons. The sample exhibits superparamagnetic features due to a distribution of crystal size and possesses magnetic hysteresis up to 350 K. Our work sets the stage for the development of spintronic materials exploiting magnetic MOF semiconductors.