Possible Room-Temperature Ferromagnetism in Self-Assembled Ensembles of Paramagnetic and Diamagnetic Molecular Semiconductors

Abstract

Owing to long spin-relaxation time and chemically customizable physical properties, molecule-based semiconductor materials like metal-phthalocyanines offer promising alternatives to conventional dilute magnetic semiconductors/oxides (DMSs/DMOs) to achieve room-temperature (RT) ferromagnetism. However, air-stable molecule-based materials exhibiting both semiconductivity and magnetic-order at RT have so far remained elusive. We present here the concept of supramolecular arrangement to accomplish possibly RT ferromagnetism. Specifically, we observe a clear hysteresis-loop (Hc ? 120 Oe) at 300 K in the magnetization versus field (M-H) plot of the self-assembled ensembles of diamagnetic Zn-phthalocyanine having peripheral F atoms (ZnFPc; S = 0) and paramagnetic Fe-phthalocyanine having peripehral H atoms (FePc; S = 1). Tauc plot of the self-assembled FePc ZnFPc ensembles showed an optical band gap of ?1.05 eV and temperature-dependent current-voltage (I-V) studies suggest semiconducting characteristics in the material. Using DFT+U quantum-chemical calculations, we reveal the origin of such unusual ferromagnetic exchange-interaction in the supramolecular FePc ZnFPc system. 2016 American Chemical Society.