Magnetic coupling between Fe(NO) spin probe ligands through diamagnetic NiII, PdII and PtII tetrathiolate bridges

Darensbourg, Marcetta Y.; Quiroz, Manuel; Xue, Shan; Jones, D. Gareth; Guo, Yisong; Pierce, Brad S.; Dunbar, Kim R.; Hall, Michael B.

doi:10.1039/d3sc01546g

Cited by 3 publications

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“…The more common, transoid trimetallic derivatives have a range of Fe−M a (M a = Ni, Pd, Pt) distances and hinge angles of 2.96−3.00 Å and 102.3−106.1°, respectively (Table S3). 30 Such metrics suggest the "space" between the metallodithiolates, and the center metal is larger in the cisoid geometry, giving such complexes their characteristic dispersed electropositive cavity.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Sulfur Lone Pairs Control Topology in Heterotrimetallic Complexes: An Experimental and Theoretical Study

Guerrero-Almaraz,

Quiroz,

Rodriguez

et al. 2023

ACS Org. Inorg. Au

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Heterotrimetallic complexes with (N 2 S 2 )M metallodithiolates, M = Ni 2+ , [Fe(NO)] 2+ , and [Co(NO)] 2+ , as bidentate chelating ligands to a central trans-Cr(NO)(MeCN) unit were characterized as the first members of a new class, NiCrNi, FeCrFe, CoCrCo. The complexes exhibit a cisoid structural topology, ascribed to the stereoactivity of the available lone pair(s) on the sulfur donors, resulting in a dispersed, electropositive pocket from the N/N and N/S hydrocarbon linkers wherein the Cr-NO site is housed. Computational studies explored alternative isomers (transoid and inverted cisoid) that suggest a combination of electronic and steric effects govern the geometrical selectivity. Electrostatic potential maps readily display the dominant electronegative potential from the sulfurs which force the NO to the electropositive pocket. The available S lone pairs work in synergy with the π-withdrawing ability of NO to lift Cr out of the S 4 plane toward the NO and stabilize the geometry. The metallodithiolate ligands bound to Cr(NO) thus find structural consistency across the three congeners. Although the dinitrosyl [(bme-dach)Co(NO)-Mo(NO)(MeCN)-(bme-dach)Co(MeCN)][PF 6 ] 2 (CoMoCo′) analogue displays chemical noninnocence and a partial Mo−Co bond toward (N 2 S 2 )Co′(NCCH 3 ) in an "asymmetric butterfly" topology [Guerrero-Almaraz, P. et al. Inorg. Chem. 2021, 60(2121), 15975−15979], the stability of the {Cr(NO)} 5 unit prohibits such bond rearrangement. Magnetism and EPR studies illustrate spin coupling across the sulfur thiolate sulfur bridges.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Sulfur Lone Pairs Control Topology in Heterotrimetallic Complexes: An Experimental and Theoretical Study

Guerrero-Almaraz,

Quiroz,

Rodriguez

et al. 2023

ACS Org. Inorg. Au

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Section: Magnetic Coupling Between Fe(no) Spin Probe Ligands Through ...mentioning

confidence: 99%

“…(B) Linear relationship between experimental J values vs the energy gap between the HOMO and HOMO-1 of the triplet states. Both figures adapted with permission from ref . Copyright 2023 Royal Society of Chemistry.…”

Section: Magnetic Coupling Between Fe(no) Spin Probe Ligands Through ...mentioning

confidence: 99%

“…Sci. 2023 , 14 , 9167–9174 . Transoid structures of [(NO)Fe(N 2 S 2 )] 2 -M 2+ have two Fe(NO) radical units at 6 Å. Superexchange via the bridging thiolates and central metal exhibit J values of −3, −23, and −124 cm –1 , reflecting enhanced covalency in M–S bonds [3 d (Ni) < 4 d (Pd) < 5 d (Pt)]. Guerrero-Almaraz, P.; Quiroz, M.; Rodriguez, D. R.; Jana, M.; Hall, M. B.; Darensbourg, M. Y.…”

Section: Key Referencesmentioning

confidence: 99%

“…(B) Spin density plots of (NO)Fe(bme-dach) showcasing signification spin delocalization on to the cis -dithiolates (isovalue 0.004). Adapted with permission from ref . Copyright 2023 Royal Society of Chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Development of (NO)Fe(N₂S₂) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach

Quiroz,

Darensbourg

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: The ubiquity of sulfur−metal connections in nature inspires the design of biand multimetallic systems in synthetic inorganic chemistry. Common motifs for biocatalysts developed in evolutionary biology include the placement of metals in close proximity with flexible sulfur bridges as well as the presence of π-acidic/delocalizing ligands. This Account will delve into the development of a (NO)Fe(N 2 S 2 ) metallodithiolate ligand that harnesses these principles. The Fe(NO) unit is the centroid of a N 2 S 2 donor field, which as a whole is capable of serving as a redox-active, bidentate S-donor ligand. Its paramagnetism as well as the ν(NO) vibrational monitor can be exploited in the development of new classes of heterobimetallic complexes. We offer four examples in which the unpaired electron on the {Fe(NO)} 7 unit is spin-paired with adjacent paramagnets in proximal and distal positions. First, the exceptional stability of the (NO)Fe(N 2 S 2 )-Fe(NO) 2 platform, which permits its isolation and structural characterization at three distinct redox levels, is linked to the charge delocalization occurring on both the Fe(NO) and the Fe(NO) 2 supports. This accommodates the formation of a rare nonheme {Fe(NO)} 8 triplet state, with a linear configuration. A subsequent FeNi complex, featuring redoxactive ligands on both metals (NO on iron and dithiolene on nickel), displayed unexpected physical properties. Our research showed good reversibility in two redox processes, allowing isolation in reduced and oxidized forms. Various spectroscopic and crystallographic analyses confirmed these states, and Mossbauer data supported the redox change at the iron site upon reduction. Oxidation of the complex produced a dimeric dication, revealing an intriguing magnetic behavior. The monomer appears as a spincoupled diradical between {Fe(NO)} 7 and the nickel dithiolene monoradical, while dimerization couples the latter radical units via a Ni 2 S 2 rhomb. Magnetic data (SQUID) on the dimer dication found a singlet ground state with a thermally accessible triplet state that is responsible for magnetism. A theoretical model built on an H 4 chain explains this unexpected ferromagnetic low-energy triplet state arising from the antiferromagnetic coupling of a four-radical molecular conglomerate. For comparison, two (NO)Fe(N 2 S 2 ) were connected through diamagnetic group 10 cations producing diradical trimetallic complexes. Antiferromagnetic coupling is observed between {Fe(NO)} 7 units, with exchange coupling constants (J) of −3, −23, and −124 cm −1 for Ni II , Pd II , and Pt II , respectively. This trend is explained by the enhanced covalency and polarizability of sulfur-dense metallodithiolate ligands. A central paramagnetic trans-Cr(NO)(MeCN) receiver unit core results in a cissoid structural topology, influenced by the stereoactivity of the lone pair(s) on the sulfur donors. This {Cr(NO)} 5 radical bridge, unlike all previous cases, finds the coupling between t...

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Magnetic Switching of Second-Harmonic Generation from Single Cerium-Based Coordination Polymer Microcrystals

Jia,

Chen,

Yang

et al. 2024

J. Phys. Chem. Lett.

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Magnetic coupling between Fe(NO) spin probe ligands through diamagnetic Ni^II, Pd^II and Pt^II tetrathiolate bridges

Abstract: The nd (n = 3–5) orbital effects on the magnetic coupling within sulfur-bridged, iso-structural, tri-metallic complexes revealed that the heavier congeners significantly enhance superexchange between distal {Fe(NO)}7 radicals: Pt ≫ Pd > Ni.

Cited by 3 publications

References 33 publications

Sulfur Lone Pairs Control Topology in Heterotrimetallic Complexes: An Experimental and Theoretical Study

Sulfur Lone Pairs Control Topology in Heterotrimetallic Complexes: An Experimental and Theoretical Study

Development of (NO)Fe(N₂S₂) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach

Magnetic Switching of Second-Harmonic Generation from Single Cerium-Based Coordination Polymer Microcrystals

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Magnetic coupling between Fe(NO) spin probe ligands through diamagnetic NiII, PdII and PtII tetrathiolate bridges

Abstract: The nd (n = 3–5) orbital effects on the magnetic coupling within sulfur-bridged, iso-structural, tri-metallic complexes revealed that the heavier congeners significantly enhance superexchange between distal {Fe(NO)}7 radicals: Pt ≫ Pd > Ni.

Cited by 3 publications

References 33 publications

Sulfur Lone Pairs Control Topology in Heterotrimetallic Complexes: An Experimental and Theoretical Study

Sulfur Lone Pairs Control Topology in Heterotrimetallic Complexes: An Experimental and Theoretical Study

Development of (NO)Fe(N2S2) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach

Magnetic Switching of Second-Harmonic Generation from Single Cerium-Based Coordination Polymer Microcrystals

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Resources

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Magnetic coupling between Fe(NO) spin probe ligands through diamagnetic Ni^II, Pd^II and Pt^II tetrathiolate bridges

Development of (NO)Fe(N₂S₂) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach