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Synthesis and Characterization of Symmetrically versus Unsymmetrically Proton-Bridged Hexa-Iron Clusters.

ABSTRACT: Syntheses and magnetic and structural characterization of hexa-iron complexes of derivatized salicylaldoximes are discussed. Complexation of Fe(BF₄)₂·6H₂O with each ligand (H₂ L1 and H₄ L2) in a methanolic-pyridine solution resulted in hexa-iron compounds (C1 and C2, respectively), which each contain two near-parallel metal triangles of [Fe₃-μ₃-O], linked by six fluoride bridges and stabilized by a hydrogen-bonded proton between the μ₃-O groups. Within each metal triangle of C2, Fe(III) ions are connected via the amine "straps" of (H₄ L2-2H). Variable-temperature magnetic susceptibility and Mössbauer data of C1 and C2 indicate the presence of dominant antiferromagnetic interactions between the high-spin (S = 5/2) Fe(III) centers. For C1, two quadrupole doublets are observed at room temperature and 5 K, consistent with structural data from which discrete but disordered [Fe₃-μ₃-O] and [Fe₃-μ₃-OH] species were inferred. For C2, a single sharp quadrupole doublet with splitting intermediate between those determined for C1 was observed, consistent with the symmetric [Fe₃-μ₃-O···H···μ₃-O-Fe₃] species inferred crystallographically from the very short μ₃-O···μ₃-O separation. The differences in the physical properties of the complexes, as seen in the Mössbauer, X-ray, and magnetic data, are attributed to the conformational flexibility imparted by the nature of the linkages between the closely related ligands.

SUBMITTER: De Silva DNT

PROVIDER: S-EPMC8246689 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Synthesis and Characterization of Symmetrically versus Unsymmetrically Proton-Bridged Hexa-Iron Clusters.

De Silva D Nirosha T DNT Dais Tyson N TN Jameson Geoffrey B GB Cutler Daniel J DJ Brechin Euan K EK Davies Casey G CG Jameson Guy N L GNL Plieger Paul G PG

ACS omega 20210615 25

Syntheses and magnetic and structural characterization of hexa-iron complexes of derivatized salicylaldoximes are discussed. Complexation of Fe(BF4)2·6H2O with each ligand (H2 L1 and H4 L2) in a methanolic-pyridine solution resulted in hexa-iron compounds (C1 and C2, respectively), which each contain two near-parallel metal triangles of [Fe3-μ3-O], linked by six fluoride bridges and stabilize ...[more]

PMID: 34235338

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Project description:A series of heteroleptic three-coordinate Cu(i) complexes bearing monodentate N-heterocyclic carbene (NHC) ligands of the type 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), and bidentate N-donor ligands of the type unsymmetrically-substituted dimethyl dipyridylamine (Me2Hdpa) and bis(mesityl)biazanaphthenequinone (mesBIAN) have been synthesized. The complexes [Cu(IPr)(3,4'-Me2Hdpa)]PF6, 1; [Cu(IPr)(3,5'-Me2Hdpa)]PF6, 2; [Cu(IPr)(3,6'-Me2Hdpa)]PF6, 3; [Cu(IPr)(mesBIAN)]PF6, 6; [Cu(SIPr)(3,4'-Me2Hdpa)]PF6, 7; [Cu(SIPr)(3,5'-Me2Hdpa)]PF6, 8; and [Cu(SIPr)(3,3'-Me2Hdpa)]PF6, 11 have been characterized by 1H and 13C NMR spectroscopies, elemental analysis, cyclic voltammetry, and photophysical studies in solid and solution phase. Single crystal X-ray structures were obtained for all complexes except 11. The crystallographic data reveal a mononuclear structure for all complexes with the copper atom ligated by one C and two N atoms. The UV-Vis absorption spectra of all dipyridylamine complexes in CH2Cl2 show a strong ligand-centered absorption band around 250 nm and a strong metal-to-ligand charge transfer (MLCT) band around 300 nm. When irradiated with UV light, the complexes exhibit strong emission maxima at 453-482 nm with photoluminescence quantum yields (PLQY) ranging from 0.21 to 0.87 in solid state. While the PLQY values are comparable to those of the symmetrical [Cu(IPr)(Me2Hdpa)]PF6 complexes, a stabilizing CH-π interaction has been reduced in the current systems. In particular, complex 3 lacks any strong CH-π interaction, but emits more efficiently than 1 and 2 wherein the interactions exist. Structural data analysis was performed to clarify the role of ligands' plane angle and the NH/CH⋯F interactions to the observed light interaction of unsymmetrical [Cu(NHC)(Me2Hdpa)]PF6 complexes. DFT calculations were performed to assist in the assignment of the electronic structure and excited state behavior of the complexes.

Dataset Information

Synthesis and Characterization of Symmetrically versus Unsymmetrically Proton-Bridged Hexa-Iron Clusters.

Publications

Synthesis and Characterization of Symmetrically <i>versus</i> Unsymmetrically Proton-Bridged Hexa-Iron Clusters.

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