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Luminescent complexes with arsane ligands have garnered considerable interest due to their uncomplicated structure and effective luminescence. Particularly, rigid monodentate arsane ligands, wherein the substituents of the arsenic atom are bridged, have proven advantageous in enhancing emission intensity. In this study, we synthesized non‐bridged, O‐bridged, S‐bridged, and O,O‐bridged triphenylarsine derivatives using the safe and efficient protocols developed in our previous work. We then created platinum dihalide (PtX2, X=Cl, Br, I) complexes with these arsane ligands. Their structures were determined through single‐crystal X‐ray diffraction, revealing significant influences on geometry by the counter anion and the arsane/phosphane ligand. Additionally, we elucidated the correlation between the ligand structure and the solid‐state emission properties [ABSTRACT FROM AUTHOR]

In this work, bisarsine oxides were evaluated as novel bridging ligands, aiming to develop practical and efficient luminescent lanthanide coordination polymers. We have synthesized one‐dimensional (1D) Eu3+ coordination polymers that incorporate bisarsine oxide bridging ligands and hexafluoroacetylacetonate anions. These polymers exhibited a denser packing of chains compared to analogous polymers bridged with bisphosphine oxides. The coordination polymers demonstrated exceptional thermal stability and substantial emission quantum yields. Additionally, the bisarsine oxides induced a pronounced polarization effect, facilitating a sensitive electric dipole transition that yields considerably narrow band red emission. Remarkably, the Eu3+ coordination polymers with bisarsine oxides maintained intense emission even at 550 K. A distinctive feature of these polymers is their heating‐induced emission enhancement observed when the temperature was increased from 300 K to 400 K. [ABSTRACT FROM AUTHOR]

This study reports unique luminescent properties of pyrene‐substituted nido‐carborate anion (PYnCA) with two counter cations, tetrabutylammonium (NBu4+) and tetraphenylphosphonium (PPh4+). It is revealed that PYnCA shows twisted intramolecular charge transfer (TICT) emission by the change of the dihedral angle between pyrene and the CcageCcage bond in the carborane unit in the excited state. Although the structure of nCA is almost same as that of ortho‐carborane (oC), the photophysical processes of both pyrene‐substituted compounds are completely different. The study also succeeds in modulating the luminescence species by counter cations in both solution and solid states. To the best of the current knowledge, this is the first report that anion‐based luminescent materials can show the different luminescent species not only in solution but also in the mechanochromic behaviors depending on the type of counter cations. This fundamental research on nCA demonstrates anion‐based emitters as a new platform for stimuli‐responsive materials. [ABSTRACT FROM AUTHOR]

We synthesized two types of the regioisomers fused by a phenylnaphthalene ring with variable connection points to the o-carborane scaffold. In this paper, we describe their photoluminescence (PL) properties and detailed photochemical mechanisms. According to the series of optical measurements, interestingly, they showed different PL characters in terms of wavelength and the dual-emission character despite that they have the common aromatic unit. Variable-temperature PL measurements and quantum chemical calculations suggested that the substitution position of aryl groups to o-carborane plays an important role in determining the energy barrier to the intramolecular charge-transfer (ICT) state at the S1 state. Finally, it is revealed that the relative position of the C–C bond of o-carborane and the aryl center should be responsible for the photophysical events of aryl-o-carboranes. [ABSTRACT FROM AUTHOR]

In this work, bisarsine oxides were evaluated as novel bridging ligands, aiming to develop practical and efficient luminescent lanthanide coordination polymers. We have synthesized one-dimensional (1D) Eu 3+ coordination polymers that incorporate bisarsine oxide bridging ligands and hexafluoroacetylacetonate anions. These polymers exhibited a denser packing of chains compared to analogous polymers bridged with bisphosphine oxides. The coordination polymers demonstrated exceptional thermal stability and substantial emission quantum yields. Additionally, the bisarsine oxides induced a pronounced polarization effect, facilitating a sensitive electric dipole transition that yields considerably narrow band red emission. Remarkably, the Eu 3+ coordination polymers with bisarsine oxides maintained intense emission even at 550 K. A distinctive feature of these polymers is their heating-induced emission enhancement observed when the temperature was increased from 300 K to 400 K., (© 2024 Wiley-VCH GmbH.)