For decades, the molecular geometry and spectroscopic identification of {Fe(NO)2}9 DNICs were limited to tetrahedral (C.N. = 4) and EPR g-value ~ 2.03, due to the inadequacy of structurally well-defined DNICs. The developed synthetic methodologies expand the scope of DNICs into non-classical square pyramidal/trigonal bipyramidal (C.N. = 5) and octahedral (C.N. = 6) {Fe(NO)2}9 DNICs as well as the accessible {Fe(NO)2}9/10 redox couples for mononuclear DNICs and [{Fe(NO)2}9/10-{Fe(NO)2}9/10] redox states for dinuclear DNICs with S/O/N ligation mode. The research of DNICs consisting of synthesis, spectroscopy and molecular catalysis to investigate their electronic structures, transformation as well as the chemically catalytic activity toward small molecules will be discussed. Specifically, the fundamental knowledge of DNICs was progressively conveyed to provide the insights of (a) the essential roles of DNICs modeling the degradation and repair of [Fe-S] clusters under the presence of NO, (b) transformation of DNIC into S-nitrosothiol (RSNO), (c) DNICs acting as NO+/NO●/NO– carrier, (d) nitrite/nitrate activation producing NO regulated by redox shuttling of {Fe(NO)2}9/10 DNICs, and (f) DNICs serving as molecular catalyst for electrocatalytic water splitting/energy-storing RWGS.

Dinitrosyl Iron Complexes (DNICs): Synthesis and spectroscopic characterization toward unveiling the catalytic roles of DNICs

253rd National Meeting (2017)

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