SHG-active luminescent thermometers based on chiral cyclometalated dicyanidoiridate(<scp>iii</scp>) complexes

Rzepiela, Jan; Liberka, Michal; Zychowicz, Mikolaj; Wang, Junhao; Tokoro, Hiroko; Piotrowska, Kinga; Baś, Sebastian; Ohkoshi, Shin-ichi; Chorazy, Szymon

doi:10.1039/d3qi02482b

Inorg. Chem. Front.

2024

DOI: 10.1039/d3qi02482b

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SHG-active luminescent thermometers based on chiral cyclometalated dicyanidoiridate(iii) complexes

Jan Rzepiela,

Michal Liberka,

Mikolaj Zychowicz

et al.

Abstract: A dicyanidoiridate(iii) complex, bearing chiral (R,R)-2-phenyl-4,5-pinenopyridine ligands, serves as a SHG-active luminescent thermometer, optimized by embedding into a heterometallic coordination polymer.

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Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active Fe^II‐W^IV(CN)₈ 3‐D Coordination Framework

Kobayashi,

Nagashima,

Ohkoshi

et al. 2024

Eur J Inorg Chem

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The effect of ligand‐based molecular alloying on spin crossover (SCO) materials has been studied using various polydentate organic ligands; however, this effect using small monodentate ligands has not been explored. To design a proper structure that can accommodate a variety of small ligands, we employed the structural matrix of a three‐dimensional cyanido‐bridged coordination framework, [FeII(Lmix)4]2[WIV(CN)8] (FeW; Lmix = a mixture of different ligands). We found that three different ligands of 4‐chloropyridine (4‐Clpy), 4‐iodopyridine (4‐Ipy), and pyrazole (pz) were able to be alloyed at the Lmix site of the FeII ion. Our obtained FeW framework had a 4‐Clpy:4‐Ipy:pz alloying ratio of 1.32:1.56:1.12 per FeII ion, and it demonstrated a gradual SCO phenomenon in response to temperature change. Furthermore, the chiral structure of FeW allows the observation of second‐harmonic generation (SHG) signal; however, the SHG signal was quite weak owing to the racemic twinning of the mirrored enantiomers. This work demonstrates that the FeII–WIV(CN)8 structural matrix provides a viable approach to investigating the molecular alloying effect of various types of small organic ligands on magneto‐optical properties.

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Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active Fe^II‐W^IV(CN)₈ 3‐D Coordination Framework

Kobayashi,

Nagashima,

Ohkoshi

et al. 2024

Eur J Inorg Chem

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show abstract

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SHG-active luminescent thermometers based on chiral cyclometalated dicyanidoiridate(iii) complexes

Abstract: A dicyanidoiridate(iii) complex, bearing chiral (R,R)-2-phenyl-4,5-pinenopyridine ligands, serves as a SHG-active luminescent thermometer, optimized by embedding into a heterometallic coordination polymer.

Cited by 1 publication

References 83 publications

Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active Fe^II‐W^IV(CN)₈ 3‐D Coordination Framework

Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active Fe^II‐W^IV(CN)₈ 3‐D Coordination Framework

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SHG-active luminescent thermometers based on chiral cyclometalated dicyanidoiridate(iii) complexes

Abstract: A dicyanidoiridate(iii) complex, bearing chiral (R,R)-2-phenyl-4,5-pinenopyridine ligands, serves as a SHG-active luminescent thermometer, optimized by embedding into a heterometallic coordination polymer.

Cited by 1 publication

References 83 publications

Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active FeII‐WIV(CN)8 3‐D Coordination Framework

Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active FeII‐WIV(CN)8 3‐D Coordination Framework

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Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active Fe^II‐W^IV(CN)₈ 3‐D Coordination Framework

Molecular Alloying of Three Different Organic Ligands within a Spin‐Transitional and SHG‐Active Fe^II‐W^IV(CN)₈ 3‐D Coordination Framework