Manganese Telluride Carbonyl Complexes: Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties

Minghuey Shieh; Yu Hsin Liu; Tien Sung Lin; Yu Chun Lin; Wen Kai Cheng; Ru Yan Lin

doi:10.1021/acs.inorgchem.0c00412

Manganese Telluride Carbonyl Complexes: Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties

Minghuey Shieh^*, Yu Hsin Liu, Tien Sung Lin, Yu Chun Lin, Wen Kai Cheng, Ru Yan Lin

^*Corresponding author for this work

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

Abstract

A novel family of five Mn-Te-CO complexes was prepared via facile syntheses: mono spirocyclic [Mn₄Te(CO)₁₆]^2- (1), four-membered Mn₂Te₂ ring-type [Mn₂Te₂(CO)₈]^2- (2), hydride-containing square pyramidal [HMn₃Te₂(CO)₉]^2- (3), and dumbbell-shaped [Mn₆Te₆(CO)₁₈]^4- (4) and [Mn₆Te₁₀(CO)₁₈]^4- (5). Electron-precise complexes 4 and 5 exhibit unusual paramagnetism arising from two types of Mn atoms in different oxidation states, as determined by X-ray photoelectron spectroscopy, electron paramagnetic resonance, and density functional theory (DFT) calculations. The structural transformations from small-sized Mn₄Te 1 and Mn₂Te₂ 2 to the largest Mn₆Te₁₀ 5 were controllable, the off/on magnetic-switched transformation between HMn₃Te₂ 3 and 5 was reversible, and the magnetic transformation between Mn₆Te₆ 4 and 5 was observed. Interestingly, the reversible dehydridation and hydridation between the HMn₃Te₂-based cluster 3 and [Mn₃Te₂(CO)₉]^- were successfully accomplished, in which the release of a high yield of H₂ was detected by gas chromatography. In addition, upon the addition of CO, cluster 3 first forms a carbonyl-inserted intermediate [HMn₃Te₂(CO)₁₀]^2- (3′), detected by the high resolution ESI-MS, which is readily transformed to a dimeric dihydrido cluster [{HMn₃Te₂(CO)₁₀}₂]^2- (6) with the introduction of O₂. These low- to high-nuclearity complexes exhibit rich redox properties with semiconducting behavior in solids, possessing low but tunable energy gaps (1.06-1.62 eV) due to efficient electron transport via nonclassical C-H···O(carbonyl) interactions. The structural nature, reversible structural transformations, controllable on/off magnetic switches, electron communication networks, and associated chemical properties for hydrogen generation are discussed in detail and supported by DFT calculations, density of states, band structures, and noncovalent interaction analyses.

Original language	English
Pages (from-to)	6923-6941
Number of pages	19
Journal	Inorganic Chemistry
Volume	59
Issue number	10
DOIs	https://doi.org/10.1021/acs.inorgchem.0c00412
Publication status	Published - 2020 May 18

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.0c00412

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Manganese Telluride Carbonyl Complexes : Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties. / Shieh, Minghuey; Liu, Yu Hsin; Lin, Tien Sung; Lin, Yu Chun; Cheng, Wen Kai; Lin, Ru Yan.

In: Inorganic Chemistry, Vol. 59, No. 10, 18.05.2020, p. 6923-6941.

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

@article{df3cf1984adc49c2a09016b38e874863,

title = "Manganese Telluride Carbonyl Complexes: Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties",

abstract = "A novel family of five Mn-Te-CO complexes was prepared via facile syntheses: mono spirocyclic [Mn4Te(CO)16]2- (1), four-membered Mn2Te2 ring-type [Mn2Te2(CO)8]2- (2), hydride-containing square pyramidal [HMn3Te2(CO)9]2- (3), and dumbbell-shaped [Mn6Te6(CO)18]4- (4) and [Mn6Te10(CO)18]4- (5). Electron-precise complexes 4 and 5 exhibit unusual paramagnetism arising from two types of Mn atoms in different oxidation states, as determined by X-ray photoelectron spectroscopy, electron paramagnetic resonance, and density functional theory (DFT) calculations. The structural transformations from small-sized Mn4Te 1 and Mn2Te2 2 to the largest Mn6Te10 5 were controllable, the off/on magnetic-switched transformation between HMn3Te2 3 and 5 was reversible, and the magnetic transformation between Mn6Te6 4 and 5 was observed. Interestingly, the reversible dehydridation and hydridation between the HMn3Te2-based cluster 3 and [Mn3Te2(CO)9]- were successfully accomplished, in which the release of a high yield of H2 was detected by gas chromatography. In addition, upon the addition of CO, cluster 3 first forms a carbonyl-inserted intermediate [HMn3Te2(CO)10]2- (3′), detected by the high resolution ESI-MS, which is readily transformed to a dimeric dihydrido cluster [{HMn3Te2(CO)10}2]2- (6) with the introduction of O2. These low- to high-nuclearity complexes exhibit rich redox properties with semiconducting behavior in solids, possessing low but tunable energy gaps (1.06-1.62 eV) due to efficient electron transport via nonclassical C-H···O(carbonyl) interactions. The structural nature, reversible structural transformations, controllable on/off magnetic switches, electron communication networks, and associated chemical properties for hydrogen generation are discussed in detail and supported by DFT calculations, density of states, band structures, and noncovalent interaction analyses.",

author = "Minghuey Shieh and Liu, {Yu Hsin} and Lin, {Tien Sung} and Lin, {Yu Chun} and Cheng, {Wen Kai} and Lin, {Ru Yan}",

note = "Funding Information: This work was supported by a grant from the Ministry of Science and Technology of Taiwan (Grant MOST 108-2113-M-003-002 to M. S.). Prof. Tien-Sung Lin was supported by multiple visiting professorship grants to C. W. Chiu and S. M. Peng of NTU from the Ministry of Sciences and Technologies of Taiwan. The authors wish to thank Prof. Ming-Kang Tsai (National Taiwan Normal University) for discussions concerning the DFT calculations. The authors also wish to thank Prof. Hui-Lung Chen (Chinese Culture University) for the discussion of the DMol calculations and NCHC of Taiwan for providing the computer time and the facilities. Our gratitude also goes to the Academic Paper Editing Clinic, NTNU. 3 Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

year = "2020",

month = may,

day = "18",

doi = "10.1021/acs.inorgchem.0c00412",

language = "English",

volume = "59",

pages = "6923--6941",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

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T1 - Manganese Telluride Carbonyl Complexes

T2 - Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties

AU - Shieh, Minghuey

AU - Liu, Yu Hsin

AU - Lin, Tien Sung

AU - Lin, Yu Chun

AU - Cheng, Wen Kai

AU - Lin, Ru Yan

N1 - Funding Information: This work was supported by a grant from the Ministry of Science and Technology of Taiwan (Grant MOST 108-2113-M-003-002 to M. S.). Prof. Tien-Sung Lin was supported by multiple visiting professorship grants to C. W. Chiu and S. M. Peng of NTU from the Ministry of Sciences and Technologies of Taiwan. The authors wish to thank Prof. Ming-Kang Tsai (National Taiwan Normal University) for discussions concerning the DFT calculations. The authors also wish to thank Prof. Hui-Lung Chen (Chinese Culture University) for the discussion of the DMol calculations and NCHC of Taiwan for providing the computer time and the facilities. Our gratitude also goes to the Academic Paper Editing Clinic, NTNU. 3 Publisher Copyright: Copyright © 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/5/18

Y1 - 2020/5/18

N2 - A novel family of five Mn-Te-CO complexes was prepared via facile syntheses: mono spirocyclic [Mn4Te(CO)16]2- (1), four-membered Mn2Te2 ring-type [Mn2Te2(CO)8]2- (2), hydride-containing square pyramidal [HMn3Te2(CO)9]2- (3), and dumbbell-shaped [Mn6Te6(CO)18]4- (4) and [Mn6Te10(CO)18]4- (5). Electron-precise complexes 4 and 5 exhibit unusual paramagnetism arising from two types of Mn atoms in different oxidation states, as determined by X-ray photoelectron spectroscopy, electron paramagnetic resonance, and density functional theory (DFT) calculations. The structural transformations from small-sized Mn4Te 1 and Mn2Te2 2 to the largest Mn6Te10 5 were controllable, the off/on magnetic-switched transformation between HMn3Te2 3 and 5 was reversible, and the magnetic transformation between Mn6Te6 4 and 5 was observed. Interestingly, the reversible dehydridation and hydridation between the HMn3Te2-based cluster 3 and [Mn3Te2(CO)9]- were successfully accomplished, in which the release of a high yield of H2 was detected by gas chromatography. In addition, upon the addition of CO, cluster 3 first forms a carbonyl-inserted intermediate [HMn3Te2(CO)10]2- (3′), detected by the high resolution ESI-MS, which is readily transformed to a dimeric dihydrido cluster [{HMn3Te2(CO)10}2]2- (6) with the introduction of O2. These low- to high-nuclearity complexes exhibit rich redox properties with semiconducting behavior in solids, possessing low but tunable energy gaps (1.06-1.62 eV) due to efficient electron transport via nonclassical C-H···O(carbonyl) interactions. The structural nature, reversible structural transformations, controllable on/off magnetic switches, electron communication networks, and associated chemical properties for hydrogen generation are discussed in detail and supported by DFT calculations, density of states, band structures, and noncovalent interaction analyses.

AB - A novel family of five Mn-Te-CO complexes was prepared via facile syntheses: mono spirocyclic [Mn4Te(CO)16]2- (1), four-membered Mn2Te2 ring-type [Mn2Te2(CO)8]2- (2), hydride-containing square pyramidal [HMn3Te2(CO)9]2- (3), and dumbbell-shaped [Mn6Te6(CO)18]4- (4) and [Mn6Te10(CO)18]4- (5). Electron-precise complexes 4 and 5 exhibit unusual paramagnetism arising from two types of Mn atoms in different oxidation states, as determined by X-ray photoelectron spectroscopy, electron paramagnetic resonance, and density functional theory (DFT) calculations. The structural transformations from small-sized Mn4Te 1 and Mn2Te2 2 to the largest Mn6Te10 5 were controllable, the off/on magnetic-switched transformation between HMn3Te2 3 and 5 was reversible, and the magnetic transformation between Mn6Te6 4 and 5 was observed. Interestingly, the reversible dehydridation and hydridation between the HMn3Te2-based cluster 3 and [Mn3Te2(CO)9]- were successfully accomplished, in which the release of a high yield of H2 was detected by gas chromatography. In addition, upon the addition of CO, cluster 3 first forms a carbonyl-inserted intermediate [HMn3Te2(CO)10]2- (3′), detected by the high resolution ESI-MS, which is readily transformed to a dimeric dihydrido cluster [{HMn3Te2(CO)10}2]2- (6) with the introduction of O2. These low- to high-nuclearity complexes exhibit rich redox properties with semiconducting behavior in solids, possessing low but tunable energy gaps (1.06-1.62 eV) due to efficient electron transport via nonclassical C-H···O(carbonyl) interactions. The structural nature, reversible structural transformations, controllable on/off magnetic switches, electron communication networks, and associated chemical properties for hydrogen generation are discussed in detail and supported by DFT calculations, density of states, band structures, and noncovalent interaction analyses.

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JO - Inorganic Chemistry

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SN - 0020-1669

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Manganese Telluride Carbonyl Complexes: Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties

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CCDC 1937276: Experimental Crystal Structure Determination

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CCDC 1937278: Experimental Crystal Structure Determination

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Manganese Telluride Carbonyl Complexes: Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties

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Datasets

CCDC 1937276: Experimental Crystal Structure Determination

CCDC 1937273: Experimental Crystal Structure Determination

CCDC 1937278: Experimental Crystal Structure Determination

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