Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer

Shihao Liu; Yi Fei Deng; Zi Yi Chen; Lingyi Meng; Xiaoyong Chang; Zhiping Zheng; Yuan Zhu Zhang

doi:10.31635/CCSCHEM.020.202000552

Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer

Shihao Liu, Yi Fei Deng, Zi Yi Chen, Lingyi Meng, Xiaoyong Chang, Zhiping Zheng, Yuan Zhu Zhang

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

Postsynthesis of the paramagnetic square-shaped complex {[(Tp*^Me)Fe(μ-CN)₂(CN)][Co(dmbpy)₂]}₂ (BPh₄)₂·6MeCN·H₂O [1, Tp*^Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyr-idine)] by grafting transition metal(II) thiocyanates via its terminal cyano groups afforded three hexanuclear [Fe₂Co₂M₂] clusters (M = Zn, 2; Co, 3; Cd, 4). The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of Fe^II,LS-Co^III,LS within the complex core. As a result, the desolvated complexes 2-4 underwent reversible and sharp thermally induced electron-transfer behavior with the transition temperatures (T_1/2) up to 312, 296, and 365 K, respectively, demonstrating an effective means of manipulating thermal barriers of the celebrated cyano-bridged square core.

Original language	English (US)
Pages (from-to)	2530-2538
Number of pages	9
Journal	CCS Chemistry
Volume	3
Issue number	9
DOIs	https://doi.org/10.31635/CCSCHEM.020.202000552
State	Published - 2021

Keywords

Cyanide
Electron transfer
Hexanuclear
Photomagnet
Postsynthesis
Square

ASJC Scopus subject areas

General Chemistry

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10.31635/CCSCHEM.020.202000552

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@article{3e3b928e175c45c3a82ff4789b354aaa,

title = "Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer",

abstract = "Postsynthesis of the paramagnetic square-shaped complex {[(Tp*Me)Fe(μ-CN)2(CN)][Co(dmbpy)2]}2 (BPh4)2·6MeCN·H2O [1, Tp*Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyr-idine)] by grafting transition metal(II) thiocyanates via its terminal cyano groups afforded three hexanuclear [Fe2Co2M2] clusters (M = Zn, 2; Co, 3; Cd, 4). The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of FeII,LS-CoIII,LS within the complex core. As a result, the desolvated complexes 2-4 underwent reversible and sharp thermally induced electron-transfer behavior with the transition temperatures (T1/2) up to 312, 296, and 365 K, respectively, demonstrating an effective means of manipulating thermal barriers of the celebrated cyano-bridged square core.",

keywords = "Cyanide, Electron transfer, Hexanuclear, Photomagnet, Postsynthesis, Square",

author = "Shihao Liu and Deng, {Yi Fei} and Chen, {Zi Yi} and Lingyi Meng and Xiaoyong Chang and Zhiping Zheng and Zhang, {Yuan Zhu}",

year = "2021",

doi = "10.31635/CCSCHEM.020.202000552",

language = "English (US)",

volume = "3",

pages = "2530--2538",

journal = "CCS Chemistry",

issn = "2096-5745",

publisher = "Chinese Chemical Society",

number = "9",

}

TY - JOUR

T1 - Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer

AU - Liu, Shihao

AU - Deng, Yi Fei

AU - Chen, Zi Yi

AU - Meng, Lingyi

AU - Chang, Xiaoyong

AU - Zheng, Zhiping

AU - Zhang, Yuan Zhu

PY - 2021

Y1 - 2021

N2 - Postsynthesis of the paramagnetic square-shaped complex {[(Tp*Me)Fe(μ-CN)2(CN)][Co(dmbpy)2]}2 (BPh4)2·6MeCN·H2O [1, Tp*Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyr-idine)] by grafting transition metal(II) thiocyanates via its terminal cyano groups afforded three hexanuclear [Fe2Co2M2] clusters (M = Zn, 2; Co, 3; Cd, 4). The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of FeII,LS-CoIII,LS within the complex core. As a result, the desolvated complexes 2-4 underwent reversible and sharp thermally induced electron-transfer behavior with the transition temperatures (T1/2) up to 312, 296, and 365 K, respectively, demonstrating an effective means of manipulating thermal barriers of the celebrated cyano-bridged square core.

AB - Postsynthesis of the paramagnetic square-shaped complex {[(Tp*Me)Fe(μ-CN)2(CN)][Co(dmbpy)2]}2 (BPh4)2·6MeCN·H2O [1, Tp*Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyr-idine)] by grafting transition metal(II) thiocyanates via its terminal cyano groups afforded three hexanuclear [Fe2Co2M2] clusters (M = Zn, 2; Co, 3; Cd, 4). The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of FeII,LS-CoIII,LS within the complex core. As a result, the desolvated complexes 2-4 underwent reversible and sharp thermally induced electron-transfer behavior with the transition temperatures (T1/2) up to 312, 296, and 365 K, respectively, demonstrating an effective means of manipulating thermal barriers of the celebrated cyano-bridged square core.

KW - Cyanide

KW - Electron transfer

KW - Hexanuclear

KW - Photomagnet

KW - Postsynthesis

KW - Square

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VL - 3

SP - 2530

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JO - CCS Chemistry

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IS - 9

ER -

Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer

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