Photoinduced Mo−CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping

The photoinduced properties of the octacoordinated complex K₄Mo^IV(CN)₈⋅2 H₂O were studied by theoretical calculations, crystallography, and optical and magnetic measurements. The crystal structure recorded at 10 K after blue light irradiation reveals an heptacoordinated Mo(CN)₇ species originating from the light-induced cleavage of one Mo−CN bond, concomitant with the photoinduced formation of a paramagnetic signal. When this complex is heated to 70 K, it returns to its original diamagnetic ground state, demonstrating full reversibility. The photomagnetic properties show a partial conversion into a triplet state possessing significant magnetic anisotropy, which is in agreement with theoretical studies. Inspired by these results, we isolated the new compound [K(crypt-222)]₃[Mo^IV(CN)₇]⋅3 CH₃CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution.     

Athermal and Soft Multi-Nanopatterning of Azopolymers: Phototunable Mechanical Properties

Imprinting nanopatterns on flexible substrates has diverse applications in advanced fabrication. However, the traditional thermal nanoimprint lithography (T-NIL) often causes shrinkage upon cooling. Here, a simple yet versatile method is introduced to fabricate multiple nanopatterns on a flexible substrate coated with an azopolymer by combining athermal nanoimprint lithography (AT-NIL) and photolithography. The azopolymer has various mechanical properties upon photoirradiation: 1) phototunable glass-transition temperatures (T_g) and concomitantly photoinduced switch from glassy plastic to viscoplastic polymer; 2) prominent modulation of viscoplasticity under light illumination at different wavelengths. Regionally selective multiple nanopatterns are conveniently fabricated, presenting angle-dependent structural color images on poly(ethylene terephthalate) (PET) substrates. The flexible, athermal and multiple nanopatterning method has the potential for on-demand fabrication of complex nanopatterns.     

Mixed‐Valence Nickel Bis(azamacrocycle) Compounds with Ghost‐Leg‐type Sheets

The fabrication of so‐called ghost‐leg sheets and their electronic properties is reported. This unique sheet structure is composed of one‐dimensional mixed‐valence nickel chains, which are linked with one another by bis(azamacrocycle) ligands. They are also topologically unique Ni^II/Ni^III mixed‐valence complexes, as confirmed by X‐ray and optical measurements. Moreover, their magnetic susceptibilities indicated two‐dimensional antiferromagnetic behavior following the Fisher 1D chain model with interchain interactions, where spins on Ni^III sites mutually interact antiferromagnetically in the sheets.     

161Dy Time‐Domain Synchrotron Mössbauer Spectroscopy for Investigating Single‐Molecule Magnets Incorporating Dy Ions

Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of ¹⁶¹Dy has been used to investigate the magnetic properties of a Dy^III‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy₃PO)₂(H₂O)₅]Br₃?2 (Cy₃PO)?2 H₂O?2 EtOH is with B₀=582.3(5) T significantly larger than that of the free‐ion Dy^III with a ⁶H_15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the Dy^III ion. This study demonstrates that ¹⁶¹Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds.