Ligand Field Strength Mediates Electron Delocalization in Octahedral [(H L)2 Fe 6 (L')m]n+ Clusters

Hernandez Sanchez, Raul; Zheng, Shao-Liang; Betley, Theodore A.

doi:10.1021/jacs.5b06453

Title: Ligand Field Strength Mediates Electron Delocalization in Octahedral [(^H L)₂ Fe ₆ (L')_m]ⁿ⁺ Clusters

Journal Article · Fri Jul 31 00:00:00 EDT 2015 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b06453· OSTI ID:1441143

Hernandez Sanchez, Raul ^[1]; Zheng, Shao-Liang ^[1]; Betley, Theodore A. ^[1]

Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology

To assess the impact of terminal ligand binding on a variety of cluster properties (redox delocalization, ground-state stabilization, and breadth of redox state accessibility), we prepared three electron-transfer series based on the hexanuclear iron cluster [(^HL)₂Fe₆(L')_m]ⁿ⁺ in which the terminal ligand field strength was modulated from weak to strong (L' = DMF, MeCN, CN). The extent of intracore M–M interactions is gauged by M–M distances, spin ground state persistence, and preference for mixed-valence states as determined by electrochemical comproportionation constants. Coordination of DMF to the [(^HL)₂Fe₆] core leads to weaker Fe–Fe interactions, as manifested by the observation of ground states populated only at lower temperatures (<100 K) and by the greater evidence of valence trapping within the mixed-valence states. Comproportionation constants determined electrochemically (K_c = 10⁴–10⁸) indicate that the redox series exhibits electronic delocalization (class II–III), yet no intervalence charge transfer (IVCT) bands are observable in the near-IR spectra. Ligation of the stronger σ donor acetonitrile results in stabilization of spin ground states to higher temperatures (~300 K) and a high degree of valence delocalization (K_c = 10²–10⁸) with observable IVCT bands. Finally, the anionic cyanide-bound series reveals the highest degree of valence delocalization with the most intense IVCT bands (K_c = 10¹²–10²⁰) and spin ground state population beyond room temperature. Lastly, across the series, at a given formal oxidation level, the capping ligand on the hexairon cluster dictates the overall properties of the aggregate, modulating the redox delocalization and the persistence of the intracore coupling of the metal sites.

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Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0008313; GM 098395

OSTI ID:: 1441143

Journal Information:: Journal of the American Chemical Society, Vol. 137, Issue 34; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 44 works

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Magnetic Properties Diagnostic for the Existence of Iron(II)-Iron(II) Bonds in Dinuclear Complexes Which Derive from Stepwise Insertion Reactions on Unsupported Iron-Aryl Bonds Klose, Alain; Solari, Euro; Floriani, Carlo Journal of the American Chemical Society, Vol. 116, Issue 20 https://doi.org/10.1021/ja00099a030	journal	October 1994
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE

CCDC 1428863: Experimental Crystal Structure Determination: TUQXAG : bis(tetra-n-butylammonium) bis(μ-N-(3-((2-aminophenyl)amino)-2-(((2-aminophenyl)amino)methyl)-2-methylpropyl)benzene-1,2-diamine)-hexacyano-hexa-iron acetonitrile solvate Space Group: P 21/c (14), Cell: a 12.459(4)Å b 17.980(5)Å c 22.485(5)Å, α 90.00° β 113.923(13)° γ 90.00° Sanchez, Raul Hernandez; Zheng, Shao-Liang; Betley, Theodore A. https://doi.org/10.5517/cc1jyvcp The current record is supplemented by this dataset	dataset	September 2015
CCDC 1428861: Experimental Crystal Structure Determination: TUQWOT : bis(μ-N-(3-((2-aminophenyl)amino)-2-(((2-aminophenyl)amino)methyl)-2-methylpropyl)benzene-1,2-diamine)-tetrakis(N,N-dimethylformamide)-hexa-iron tetrakis(tetrafluoroborate) N,N-dimethylformamide solvate Space Group: P 21/n (14), Cell: a 17.812(2)Å b 12.6705(15)Å c 20.346(2)Å, α 90.00° β 95.7441(19)° γ 90.00° Hernandez Sanchez, Raul; Zheng, Shao-Liang; Betley, Theodore A. https://doi.org/10.5517/cc1jyv9m The current record is supplemented by this dataset	dataset	September 2015
CCDC 1428864: Experimental Crystal Structure Determination: TUQXEK : sodium bis(μ-N-(3-((2-aminophenyl)amino)-2-(((2-aminophenyl)amino)methyl)-2-methylpropyl)benzene-1,2-diamine)-hexacyano-hexa-iron acetonitrile solvate octahydrate Sánchez, Raúl Hernández; Zheng, Shao-Liang; Betley, Theodore https://doi.org/10.5517/cc1jyvdq The current record is supplemented by this dataset	dataset	September 2015
CCDC 1428859: Experimental Crystal Structure Determination: TUQWEJ : bis(μ-N-(3-((2-aminophenyl)amino)-2-(((2-aminophenyl)amino)methyl)-2-methylpropyl)benzene-1,2-diamine)-tetrakis(N,N-dimethylformamide)-hexa-iron bis(hexafluorophosphate) N,N-dimethylformamide solvate monohydrate Sánchez, Raúl Hernández; Zheng, Shao-Liang; Betley, Theodore A. https://doi.org/10.5517/cc1jyv7k The current record is supplemented by this dataset	dataset	September 2015
CCDC 1428862: Experimental Crystal Structure Determination: TUQWUZ : tris(tetraethylammonium) bis(μ-N-(3-((2-aminophenyl)amino)-2-(((2-aminophenyl)amino)methyl)-2-methylpropyl)benzene-1,2-diamine)-hexacyano-hexa-iron acetonitrile solvate Sánchez, Raúl Hernández; Zheng, Shao-Liang; Betley, Theodore A. https://doi.org/10.5517/cc1jyvbn The current record is supplemented by this dataset	dataset	September 2015
CCDC 1428860: Experimental Crystal Structure Determination: TUQWIN : bis(μ-N-(3-((2-aminophenyl)amino)-2-(((2-aminophenyl)amino)methyl)-2-methylpropyl)benzene-1,2-diamine)-tetrakis(N,N-dimethylformamide)-hexa-iron tris(hexafluorophosphate) N,N-dimethylformamide solvate Sánchez, Raúl Hernández; Zheng, Shao-Liang; Betley, Theodore https://doi.org/10.5517/cc1jyv8l The current record is supplemented by this dataset	dataset	September 2015

Title: Ligand Field Strength Mediates Electron Delocalization in Octahedral [(H L)2 Fe 6 (L')m]n+ Clusters

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