Organic molecules with switchable magnetic properties have extensively technological applications due to the fact that magnetic conversion can be realized through diverse methods. In particular, the redox-induced magnetic reversal is easy to accomplish and exhibits promising application in the field of magnetic materials, and thus it is an imperative task to find magnetism-switchable systems. Herein, we computationally design two couples of nitroxy–pyrazinyl–nitroxy diradicals in which two nitroxy radical groups are connected to a redox-active pyrazinyl coupler in the para or meta modes. We find that the magnetic conversion can occur from ferromagnetic to antiferromagnetic exchange coupling or vice versa by means of the redox method in these designed magnetic organic molecules, and their magnetic exchange coupling constants are considerably large no matter for ferromagnetic or antiferromagnetic couplings, as evidenced at both the B3LYP and M06-2X levels of theory. Analyses indicate that redox-induced structural change of the coupler leads to conversion of its aromaticity and considerable spin delocalization from the π-conjugated structure and spin polarization from non-Kekule structure, which thus determine the spin coupling between two spin centers in the magnetic molecules. In addition, the spin alternation rule, singly occupied molecular orbital (SOMO) effect, and SOMO–SOMO energy splitting of triplet state are utilized to analyze the diradical characters of the molecules, suggesting effective tools for predicting molecular ground states (ferromagnetic, antiferromagnetic, or nonmagnetic). This work provides helpful information for the rational design of promising organic magnetic switches.

Proton-induced magnetic enhancement in an organic diradical is an appealing phenomenon. Here, taking two nitroxide groups as spin sources, we predict the magnetic properties of the trans and cis forms of azobenzene (AB)-bridged diradicals in which the central −NN– unit can undergo single protonation to convert to its protonated counterpart or vice versa. The calculated results for these two pairs of diradicals (protonated versus unprotonated trans and cis forms) indicate that the signs of their magnetic coupling constants J do not change, but the magnitudes remarkably increase after protonation from −716.4 to −1787.1 cm–1 for the trans form and from −388.1 to −1227.9 cm–1 for the cis form, respectively. Such noticeable magnetic enhancements induced by protonation are mainly attributed to the strong mediating role of the coupler AB between two radical groups through its lowest unoccupied molecular orbital (LUMO) with a lower energy level after protonation. The planar structure for the protonated trans diradical and two reduced CCNN torsional angles due to protonation for the cis one are responsible for the significant magnetic enhancements. Protonation not only supports the development of π conjugation among the spin groups and coupler but also creates a very favorable condition for spin transmission through the coupler AB LUMO by lowering the LUMO energy level and improving spin polarization and charge delocalization and thus enhances the spin coupling effectively. In addition, different spin sources and linking modes of the radical groups are also considered to confirm our conclusions, and the possibilities of protonation of such diradical systems are further discussed. The studied diradicals could be the promising candidates for the rational design of magnetic molecular switches.

Cu nanowires–Ag heterostructures are prepared using the as-prepared rough Cu wires as “substrate”, which exhibit an excellent catalytic activity.

The resultant ternary spherical Ag–Cu2O/rGO composite with complex heterostructures exhibited excellent photocatalytic activity and higher stability.

While the conductance behavior of carbon-based couplers has been successfully investigated, insight into the magnetic properties of such carbon-based molecule coupled diradical systems is still scarce, and especially the structural effect of such couplers on the magnetic properties is poorly understood. The present work reports three different interference effects on the magnetic properties of carbon-based molecule coupled nitroxide diradicals: twisting, sideways group, and position effects. DFT calculations reveal that (i) torsion does not change their broken-symmetry singlet ground state and antiferromagnetic coupling, but decreases their magnetism; (ii) different linkages of two radical moieties result in different ground states and thus different magnetisms, depending on a combination of meta-sites and para-sites; (iii) the antiferromagnetic coupling with a broken-symmetry singlet ground state is not changed by adding sideways groups, but the coupling magnitude can be tuned by modifying the side-bridge. Discussions on geometries, magnetic properties, SOMO-SOMO splittings, and spin density distributions are made to clarify relevant magnetic behaviors. Clearly, the findings concerning the regulation of the diradicalized material molecules through modifying the carbon-based bridges provide a comprehensive understanding of the magnetism of such carbon-based diradicals and new prospects for the design of building blocks of magnetic functional molecular materials.

We theoretically design four diaza‐benzo[k]tetraphene‐based diradical isomers (1, 2, 3, and 4) with two nitroxide (NO) radical groups as spin sources. The calculations at the B3LYP/6‐311++G(d,p) level suggest that the diaza doping can induce the aromaticity changes and the CC bond rearrangements and, thus, remarkably affect their magnetic coupling magnitudes and even characteristics (ferromagnetic vs. antiferromagnetic). More interestingly, different diaza‐doping positions can lead to distinctly different effects, and further dielectron‐oxidation can also noticeably change the magnetic coupling magnitudes from −919.9 cm−1 (1) to −158.3 cm−1 (1 2+) or from −105.1 cm−1 (3) to −918.9 cm−1 (3 2+) or induce the magnetic conversions from nonmagnetism (2) to antiferromagnetism (2 2+, −140.1 cm−1) or from ferromagnetism (4, 108.9 cm−1) to antiferromagnetism (4 2+, −462.5 cm−1). Good matching of two singly occupied molecular orbitals (SOMOs) of the NO groups with the highest occupied molecular orbital (HOMO) of the coupler (for 1), or with the lowest unoccupied molecular orbital (LUMO) of the coupler (for 3 2+ and 4 2+), available Kekulé structure (for 2), aromaticity variations are responsible to strong magnetic couplings. Besides, the HOMO‐LUMO energy gaps of the couplers also considerably affect the magnetic couplings. This work may open a new route for the rational design of the diaza‐benzo[k]tetraphene‐based magnetic molecular modulators or switches.

While the photoelectrochemical behavior of azapentacene has been investigated successfully, insight into the dynamic electronic properties of azapentacene triggered by different energy pulses is very scarce. The present work reports a fascinating phenomenon about potential diradical character governed by structural vibrations in hexazapentacene. In complete contrast to the static equilibrium configuration of hexazapentacene without diradical character, due to the vibration-based structural perturbation, DFT calculations show that some of the transient configurations possess diradical character and thus magnetism, which exhibit different periodic pulse behavior in time evolution. Since each vibrational mode refers to two distortion ways (positive/negative distortions from equilibrium configuration), 7 different possibilities are observed for the vibrationinduced diradical character for all vibrational modes (e.g., a combination of nonradical, singlet diradical, or triplet diradical for positive distortion and those of for negative distortion for each vibrational mode). This intriguing diradical character is rationalized by structural distortions with considerable changes of some energy quantities. The structural distortions cause the HOMO energy raising and LUMO energy lowering and thus an efficient reduction of the HOMO−LUMO energy gap and singlet−triplet gap of the system, which are favorable to the formation of the broken-symmetry open-shell singlet or triplet states. The periodic pulsing behavior is attributed to persistent molecular vibrations and is thus vibrational mode controlled. Compared with pentacene, the remarked effects of nitrogen substitution on the diradical properties and their pulsing behaviors are mainly due to the decreases of both the HOMO and the LUMO energies and considerable narrowing of their gaps in the vibrationsdistorted configurations. This intriguing potential diradical character and its different dynamic behavior suggest hexazapentacene potential applications as promising building blocks in the rational design of novel electromagnetic materials because of its controllable magnetism through energy pulses. This work provides comprehensive understanding of the nature of dynamic variations of the electronic structures and properties of the nitrogen-rich acene derivatives and other materials molecules.

The as-obtained Cu/rGO hybrids possess excellent air stability, a higher catalytic efficiency to the reduction of p-nitrophenol and exhibit surface-enhanced Raman scattering activity.