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Herein, the electron conductivities of [18]annulene and its derivatives are theoretically examined as a molecular parallel circuit model consisting of two linear polyenes. Their electron conductivities are estimated by elastic scattering Green's function (ESGF) theory and density functional theory (DFT) methods. The calculated conductivity of the [18]annulene does not follow the classical conductivity, i.e., Ohm's law, suggesting the importance of a quantum interference effect in single molecules. By introducing electron-withdrawing groups into the annulene framework, on the other hand, a spin-polarized electronic structure appears, and the quantum interference effect is significantly suppressed. In addition, the total current is affected by the spin polarization because of the asymmetry in the coupling constant between the molecule and electrodes. From these results, it is suggested that the electron conductivity as well as the quantum interference effect of π-conjugated molecular systems can be designed using their open-shell nature, which is chemically controlled by the substituents.

Porous magnets that undergo a magnetic phase transition in response to gaseous adsorbates are desirable for the development of sustainable sensing and memory devices. Familiar gases such as O 2 and CO 2 are one class of target adsorbates because of their close association with life sciences and environmental issues; however, it is not easy to develop magnetic devices that respond to these ubiquitous gases. To date, only three examples of gas-responsive magnetic phase transitions have been demonstrated: (i) from a ferrimagnet to an antiferromagnet, (ii) its vice versa (i.e., change of magnetic phase), and (iii) from a ferrimagnet to a paramagnet (i.e., erasure of the magnetic phase). However, the creation of a magnet, meaning the change from a nonmagnet to a magnet by O 2 or CO 2 gas adsorption and magnetic switching by this phenomenon have not yet been explored. Herein, we report a CO 2 -induced antiferromagnet modified from a paramagnetic charge-flexible layered compound, [{Ru 2 (2,4-F 2 PhCO 2 ) 4 } 2 TCNQ(OEt) 2 ] ( 1 ; 2,4-F 2 PhCO 2 - = 2,4-difluorobenzoate; TCNQ(OEt) 2 = 2,5-diethoxy-7,7,8,8-tetracyanoquinodimethane), where three molar equivalents of CO 2 was accommodated at a CO 2 pressure of 100 kPa. The magnetic change originates from charge fluctuation due to the transfer of electrons moving from the electron-donor to the electron-acceptor unit or vice versa, resulting in a change in the electron distribution induced by CO 2 adsorption/desorption in the donor-acceptor-type charge transfer framework. Owing to the reversible electronic state change upon CO 2 adsorption/desorption, these magnetic phases are switched, accompanied by modification of the electrical conductivity, which is boosted by the CO 2 accommodation. This is the first example of the creation of a CO 2 -responsive magnet, which is promising for novel molecular multifunctional devices.

Partial charge fluctuations in the charge-ordered state of a material, often triggered by structural disorders and/or defects, can significantly alter its physical characteristics, such as magnetic long-range ordering. However, it is difficult to post-chemically fix such accidental partial fluctuations to reconstruct a uniform charge-ordered state. Herein, we report CO 2 -aided charge ordering demonstrated in a CO 2 -post-captured layered magnet, [{Ru 2 (o-ClPhCO 2 ) 4 } 2 {TCNQ(OMe) 2 }] ⋅ CO 2 (1⊃CO 2 ; o-ClPhCO 2 - =ortho-chlorobenzoate; TNCQ(OMe) 2 =2,5-dimethoxy-7,7,8,8-tetracyanoquinodimethane). Pristine porous layered magnet 1 had a partially charge-fluctuated ordered state, which provided ferrimagnetic ordering at T C =65 K. Upon loading CO 2 , 1 adsorbed one mole of CO 2 , forming 1⊃CO 2 , and raising T C to 100 K. This was because of the vanishing charge fluctuations without significantly changing the framework structure. This research illustrates the post-accessible host-guest chemistry delicately combined with charge, spin, and lattice ordering in a spongy magnet. Furthermore, it highlights how this innovative approach opens up new possibilities for technology and nanoscale magnetism manipulation., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Unique spin-spin (magnetic) interactions, ring-size effects on ground-state spin multiplicity, and in-plane aromaticity has been found in localized 1,3-diradicals embedded in curved benzene structures such as cycloparaphenylene (CPP). In this study, we characterized the magnetic interactions in a tetraradical consisting of two localized 1,3-diradical units connected by p-quaterphenyl within a curved CPP skeleton by electron paramagnetic resonance (EPR) spectroscopy and quantum chemical calculations. Persistent triplet species with zero-field splitting parameters similar to those of a triplet 1,3-diphenylcyclopentane-1,3-diyl diradical were observed by continuous wave (CW) or pulsed X-band EPR measurements. The quintet state derived from the ferromagnetic interaction between the two triplet diradical moieties was not detected at 20 K under glassy matrix conditions. At the B3LYP/6-31G(d) level of theory, the singlet state was lower in energy than the triplet and quintet states. These findings will aid in the development of open-shell species for material science application., (© 2023 Wiley-VCH GmbH.)

The effect of hydrogen bonds around the active site of Anabaena [2Fe-2S] ferredoxin (Fd) on a vertical ionization potential of the reduced state ( IP(red) ) is examined based on the density functional theory (DFT) calculations. The results indicate that a single hydrogen bond increases the relative stability of the reduced state, and shifts IP(red) to a reductive side by 0.31-0.33 eV, regardless of the attached sulfur atoms. In addition, the IP(red) value can be changed by the number of hydrogen bonds around the active site. The results also suggest that the redox potential of [2Fe-2S] Fd is controlled by the number of hydrogen bonds because IP(red) is considered to be a major factor in the redox potential. Furthermore, there is a possibility that the redox potentials of artificial iron-sulfur clusters can be finely controlled by the number of the hydrogen bonds attached to the sulfur atoms of the cluster.