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

Research output: Contribution to journalArticle

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 languageEnglish
Pages (from-to)6923-6941
Number of pages19
JournalInorganic Chemistry
Volume59
Issue number10
DOIs
Publication statusPublished - 2020 May 18

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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