π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive materials for (opto)­electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure, and conductivity in π-conjugated 2D COFs remains elusive. Here, we report a detailed characterization for the electronic properties of two novel samples consisting of Zn– and Cu–phthalocyanine-based pyrazine-linked 2D COFs. These 2D COFs are synthesized by condensation of metal–phthalocyanine (M = Zn and Cu) and pyrene derivatives. The obtained polycrystalline-layered COFs are p-type semiconductors both with a band gap of ∼1.2 eV. A record device-relevant mobility up to ∼5 cm2/(V s) is resolved in the dc limit, which represents a lower threshold induced by charge carrier localization at crystalline grain boundaries. Hall effect measurements (dc limit) and terahertz (THz) spectroscopy (ac limit) in combination with density functional theory (DFT) calculations demonstrate that varying metal center from Cu to Zn in the phthalocyanine moiety has a negligible effect in the conductivity (∼5 × 10–7 S/cm), charge carrier density (∼1012 cm–3), charge carrier scattering rate (∼3 × 1013 s–1), and effective mass (∼2.3m 0) of majority carriers (holes). Notably, charge carrier transport is found to be anisotropic, with hole mobilities being practically null in-plane and finite out-of-plane for these 2D COFs.

Metal–organic frameworks (MOFs) have so far been highlighted for their potential roles in catalysis, gas storage and separation. However, the realization of high electrical conductivity (>10−3 S cm−1) and magnetic ordering in MOFs will afford them new functions for spintronics, which remains relatively unexplored. Here, we demonstrate the synthesis of a two-dimensional MOF by solvothermal methods using perthiolated coronene as a ligand and planar iron-bis(dithiolene) as linkages enabling a full π-d conjugation. This 2D MOF exhibits a high electrical conductivity of ~10 S cm−1 at 300 K, which decreases upon cooling, suggesting a typical semiconductor nature. Magnetization and 57Fe Mössbauer experiments reveal the evolution of ferromagnetism within nanoscale magnetic clusters below 20 K, thus evidencing exchange interactions between the intermediate spin S = 3/2 iron(III) centers via the delocalized π electrons. Our results illustrate that conjugated 2D MOFs have potential as ferromagnetic semiconductors for application in spintronics.

The emergence of smart electronics, human friendly robotics and supplemented or virtual reality demands electronic skins with both tactile and touchless perceptions for the manipulation of real and virtual objects. Here, we realize bifunctional electronic skins equipped with a compliant magnetic microelectromechanical system able to transduce both tactile—via mechanical pressure—and touchless—via magnetic fields—stimulations simultaneously. The magnetic microelectromechanical system separates electric signals from tactile and touchless interactions into two different regions, allowing the electronic skins to unambiguously distinguish the two modes in real time. Besides, its inherent magnetic specificity overcomes the interference from non-relevant objects and enables signal-programmable interactions. Ultimately, the magnetic microelectromechanical system enables complex interplay with physical objects enhanced with virtual content data in augmented reality, robotics, and medical applications.

ZnO films were prepared by pulsed laser deposition on a-plane sapphire substrates under N2 atmosphere. Ferromagnetic loops were obtained with the superconducting quantum interference device at room temperature, which indicate a Curie temperature much above room temperature. No clear ferromagnetism was observed in intentionally Cu-doped ZnO films. This excludes that Cu doping into ZnO plays a key role in tuning the ferromagnetism in ZnO. 8.8% negative magnetoresistance probed at 5K at 60kOe on ferromagnetic ZnO proves the lack of s-d exchange interaction. Anomalous Hall effect (AHE) was observed in ferromagnetic ZnO as well as in nonferromagnetic Cu-doped ZnO films, indicating that AHE does not uniquely prove ferromagnetism. The observed ferromagnetism in ZnO is attributed to intrinsic defects.

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 K 3 Fe 2 [( 2,3,9,10,16,17,23,24 -octahydroxy phthalocyaninato)Fe] (K 3 Fe 2 [PcFe-O 8 ]) 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 cm 2 V −1 s −1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and 57 Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K 3 Fe 2 [PcFe-O 8 ] 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.