Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand

Diana Temerova; Tai Che Chou; Kristina S. Kisel; Toni Eskelinen; Niko Kinnunen; Janne Jänis; Antti J. Karttunen; Pi-Tai Chou; Igor O. Koshevoy

doi:10.1021/acs.inorgchem.2c02867

Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand

Diana Temerova, Tai Che Chou, Kristina S. Kisel, Toni Eskelinen, Niko Kinnunen, Janne Jänis, Antti J. Karttunen^*, Pi-Tai Chou^*, Igor O. Koshevoy^*

^*Corresponding author for this work

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Abstract

The phosphonium-decorated phenanthro-imidazolyl pyridine ligand, LP⁺Br, readily reacts with zinc(II) and cadmium(II) bromides to give inorganic-organic zero-dimensional compounds [LP⁺ZnBr₂]₂[ZnBr₄] (1) and [(LP⁺)₂Cd₂Br₄][CdBr₄] (2), respectively, upon crystallization. These salts are moderately fluorescent in the solid state under ambient conditions (λ_em = 458 nm, φ_em = 0.11 for 1; λ_em = 460 nm, φ_em = 0.13 for 2). Their emission results from spin-allowed electronic transitions localized on the organic component with the negligible effect of [MBr₄]^2- and MBr₂ units. Contrary to ionic species 1 and 2, lead(II) bromide affords a neutral and water-stable complex [(LP⁺)₂Pb₃Br₈] (3), showing weak room-temperature phosphorescence arising from spin-orbit coupling due to the heavy atom effect. The emission, which is substantially enhanced for the amorphous sample of 3 (λ_em = 575 nm, φ_em = 0.06), is assigned to the intraligand triplet excited state, which is a rare phenomenon among Pb(II) molecular materials.

Original language	English
Pages (from-to)	19220–19231
Journal	Inorganic Chemistry
Volume	61
Issue number	48
Early online date	22 Nov 2022
DOIs	https://doi.org/10.1021/acs.inorgchem.2c02867
Publication status	Published - 5 Dec 2022
MoE publication type	A1 Journal article-refereed

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@article{352be2d4c8844e1282cf57833117d9af,

title = "Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand",

abstract = "The phosphonium-decorated phenanthro-imidazolyl pyridine ligand, LP+Br, readily reacts with zinc(II) and cadmium(II) bromides to give inorganic-organic zero-dimensional compounds [LP+ZnBr2]2[ZnBr4] (1) and [(LP+)2Cd2Br4][CdBr4] (2), respectively, upon crystallization. These salts are moderately fluorescent in the solid state under ambient conditions (λem = 458 nm, φem = 0.11 for 1; λem = 460 nm, φem = 0.13 for 2). Their emission results from spin-allowed electronic transitions localized on the organic component with the negligible effect of [MBr4]2- and MBr2 units. Contrary to ionic species 1 and 2, lead(II) bromide affords a neutral and water-stable complex [(LP+)2Pb3Br8] (3), showing weak room-temperature phosphorescence arising from spin-orbit coupling due to the heavy atom effect. The emission, which is substantially enhanced for the amorphous sample of 3 (λem = 575 nm, φem = 0.06), is assigned to the intraligand triplet excited state, which is a rare phenomenon among Pb(II) molecular materials.",

author = "Diana Temerova and Chou, {Tai Che} and Kisel, {Kristina S.} and Toni Eskelinen and Niko Kinnunen and Janne J{\"a}nis and Karttunen, {Antti J.} and Pi-Tai Chou and Koshevoy, {Igor O.}",

note = "Funding Information: Financial support from the Academy of Finland (decision 317903, I.O.K.; decision 340584, T.E. and A.J.K.; Flagship Programme, Photonics Research and Innovation PREIN, decision 320166) and computational resources from the Finnish IT Center for Science (CSC) are gratefully acknowledged. Publisher Copyright: {\textcopyright} 2022 The Authors. Published by American Chemical Society.",

year = "2022",

month = dec,

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doi = "10.1021/acs.inorgchem.2c02867",

language = "English",

volume = "61",

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journal = "Inorganic Chemistry",

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T1 - Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand

AU - Temerova, Diana

AU - Chou, Tai Che

AU - Kisel, Kristina S.

AU - Eskelinen, Toni

AU - Kinnunen, Niko

AU - Jänis, Janne

AU - Karttunen, Antti J.

AU - Chou, Pi-Tai

AU - Koshevoy, Igor O.

N1 - Funding Information: Financial support from the Academy of Finland (decision 317903, I.O.K.; decision 340584, T.E. and A.J.K.; Flagship Programme, Photonics Research and Innovation PREIN, decision 320166) and computational resources from the Finnish IT Center for Science (CSC) are gratefully acknowledged. Publisher Copyright: © 2022 The Authors. Published by American Chemical Society.

PY - 2022/12/5

Y1 - 2022/12/5

N2 - The phosphonium-decorated phenanthro-imidazolyl pyridine ligand, LP+Br, readily reacts with zinc(II) and cadmium(II) bromides to give inorganic-organic zero-dimensional compounds [LP+ZnBr2]2[ZnBr4] (1) and [(LP+)2Cd2Br4][CdBr4] (2), respectively, upon crystallization. These salts are moderately fluorescent in the solid state under ambient conditions (λem = 458 nm, φem = 0.11 for 1; λem = 460 nm, φem = 0.13 for 2). Their emission results from spin-allowed electronic transitions localized on the organic component with the negligible effect of [MBr4]2- and MBr2 units. Contrary to ionic species 1 and 2, lead(II) bromide affords a neutral and water-stable complex [(LP+)2Pb3Br8] (3), showing weak room-temperature phosphorescence arising from spin-orbit coupling due to the heavy atom effect. The emission, which is substantially enhanced for the amorphous sample of 3 (λem = 575 nm, φem = 0.06), is assigned to the intraligand triplet excited state, which is a rare phenomenon among Pb(II) molecular materials.

AB - The phosphonium-decorated phenanthro-imidazolyl pyridine ligand, LP+Br, readily reacts with zinc(II) and cadmium(II) bromides to give inorganic-organic zero-dimensional compounds [LP+ZnBr2]2[ZnBr4] (1) and [(LP+)2Cd2Br4][CdBr4] (2), respectively, upon crystallization. These salts are moderately fluorescent in the solid state under ambient conditions (λem = 458 nm, φem = 0.11 for 1; λem = 460 nm, φem = 0.13 for 2). Their emission results from spin-allowed electronic transitions localized on the organic component with the negligible effect of [MBr4]2- and MBr2 units. Contrary to ionic species 1 and 2, lead(II) bromide affords a neutral and water-stable complex [(LP+)2Pb3Br8] (3), showing weak room-temperature phosphorescence arising from spin-orbit coupling due to the heavy atom effect. The emission, which is substantially enhanced for the amorphous sample of 3 (λem = 575 nm, φem = 0.06), is assigned to the intraligand triplet excited state, which is a rare phenomenon among Pb(II) molecular materials.

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U2 - 10.1021/acs.inorgchem.2c02867

DO - 10.1021/acs.inorgchem.2c02867

M3 - Article

AN - SCOPUS:85142537463

VL - 61

SP - 19220

EP - 19231

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 48

ER -

Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand

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CCDC 2195809: Experimental Crystal Structure Determination

CCDC 2195810: Experimental Crystal Structure Determination

CCDC 2195808: Experimental Crystal Structure Determination

Optical and photophysical properties of luminescent coinage-metal compounds

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Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand

Abstract

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CCDC 2195809: Experimental Crystal Structure Determination

CCDC 2195810: Experimental Crystal Structure Determination

CCDC 2195808: Experimental Crystal Structure Determination

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Optical and photophysical properties of luminescent coinage-metal compounds

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