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Structural and Electronic Responses to the Three Redox Levels of Fe(NO)N₂ S₂ -Fe(NO)₂.

ABSTRACT: The nitrosylated diiron complexes, Fe₂ (NO)₃ , of this study are interpreted as a mono-nitrosyl Fe(NO) unit, MNIU, within an N₂ S₂ ligand field that serves as a metallodithiolate ligand to a dinitrosyl iron unit, DNIU. The cationic Fe(NO)N₂ S₂ ⋅Fe(NO)₂ ⁺ complex, 1⁺ , of Enemark-Feltham electronic notation {Fe(NO)}⁷ -{Fe(NO)₂ }⁹ , is readily obtained via myriad synthetic routes, and shown to be spin coupled and diamagnetic. Its singly and doubly reduced forms, {Fe(NO)}⁷ -{Fe(NO)₂ }¹⁰ , 1⁰ , and {Fe(NO)}⁸ -{Fe(NO)₂ }¹⁰ , 1^- , were isolated and characterized. While structural parameters of the DNIU are largely unaffected by redox levels, the MNIU readily responds; the neutral, S= 1/2 , complex, 1⁰ , finds the extra electron density added into the DNIU affects the adjacent MNIU as seen by the decrease its Fe-N-O angle (from 171° to 149°). In contrast, addition of the second electron, now into the MNIU, returns the Fe-N-O angle to 171° in 1^- . Compensating shifts in Fe_MNIU distances from the N₂ S₂ plane (from 0.518 to 0.551 to 0.851 Å) contribute to the stability of the bimetallic complex. These features are addressed by computational studies which indicate that the MNIU in 1^- is a triplet-state {Fe(NO)}⁸ with strong spin polarization in the more linear FeNO unit. Magnetic susceptibility and parallel mode EPR results are consistent with the triplet state assignment.

SUBMITTER: Ghosh P

PROVIDER: S-EPMC8359741 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Structural and Electronic Responses to the Three Redox Levels of Fe(NO)N2 S2 -Fe(NO)2.

Ghosh Pokhraj P Ding Shengda S Quiroz Manuel M Bhuvanesh Nattamai N Hsieh Chung-Hung CH Palacios Philip M PM Pierce Brad S BS Darensbourg Marcetta Y MY Hall Michael B MB

Chemistry (Weinheim an der Bergstrasse, Germany) 20181009 60

The nitrosylated diiron complexes, Fe2 (NO)3 , of this study are interpreted as a mono-nitrosyl Fe(NO) unit, MNIU, within an N2 S2 ligand field that serves as a metallodithiolate ligand to a dinitrosyl iron unit, DNIU. The cationic Fe(NO)N2 S2 ⋅Fe(NO)2 + complex, 1+ , of Enemark-Feltham electronic notation {Fe(NO)}7 -{Fe(NO)2 }9 , is readily obtained via myriad synt ...[more]

PMID: 30216575

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Project description:Lead-free double perovskites have emerged as stable and non-toxic alternatives to Pb-halide perovskites. Herein, the synthesis of Fe-doped Cs2 AgBiCl6 lead-free double perovskites are reported that display blue emission using an antisolvent method. The crystal structure, morphology, optical properties, band structure, and stability of the Fe-doped double perovskites were investigated systematically. Formation of the Fe-doped Cs2 AgBiCl6 double perovskite is confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. XRD and thermo-gravimetric analysis (TGA) shows that the Cs2 AgBiCl6 double perovskite has high structural and thermal stability, respectively. Field emission scanning electron microscopy (FE-SEM) analysis revealed the formation of dipyramidal shape Cs2 AgBiCl6 crystals. Furthermore, energy-dispersive X-ray spectroscopy (EDS) mapping shows the overlapping of Cs, Bi, Ag, Fe, and Cl elements and homogenous incorporation of Fe in Cs2 AgBiCl6 double perovskite. The Fe-doped Cs2 AgBiCl6 double perovskite shows a strong absorption at 380 nm. It extends up to 700 nm, suggesting that sub-band gap states transition may originate from the surface defect of the doped perovskite material. The radiative kinetics of the crystals was studied using the time-correlated single-photon counting (TCSPC) technique. Lattice parameters and band gap value of the Fe-doped Cs2 AgBiCl6 double perovskites predicted by the density functional theory (DFT) calculations are confirmed by XRD and UV/Visible spectroscopy analysis. Time-dependent photo-response characteristics of the Fe-doped Cs2 AgBiCl6 double perovskite show fast response and recovery time of charge carriers. We believe that the successful incorporation of Fe in lead-free, environmentally friendly Cs2 AgBiCl6 double perovskite can open a new class of doped double perovskites with significant potential optoelectronics devices fabrication and photocatalytic applications.

Dataset Information

Structural and Electronic Responses to the Three Redox Levels of Fe(NO)N₂ S₂ -Fe(NO)₂.

Publications

Structural and Electronic Responses to the Three Redox Levels of Fe(NO)N<sub>2</sub> S<sub>2</sub> -Fe(NO)<sub>2</sub>.

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