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Synthesis and Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion.

ABSTRACT: Bis(1-(4-tolyl)-carboran-2-yl)-(4-tolyl)-borane [(1-(4-MeC₆ H₄ )-closo-1,2-C₂ B₁₀ H₁₀ -2-)₂ (4-MeC₆ H₄ )B] (1), a new bis(o-carboranyl)-(R)-borane was synthesised by lithiation of the o-carboranyl precursor and subsequent salt metathesis reaction with (4-tolyl)BBr₂ . Cyclic voltammetry experiments on 1 show multiple distinct reduction events with a one-electron first reduction. In a selective reduction experiment the corresponding paramagnetic radical anion 1^.- was isolated and characterized. Single-crystal structure analyses allow an in-depth comparison of 1, 1^.- , their calculated geometries, and the S₁ excited state of 1. Photophysical studies of 1 show a charge transfer (CT) emission with low quantum yield in solution but a strong increase in the solid state. TD-DFT calculations were used to identify transition-relevant orbitals.

SUBMITTER: Krebs J

PROVIDER: S-EPMC8252506 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Synthesis and Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion.

Krebs Johannes J Haehnel Martin M Krummenacher Ivo I Friedrich Alexandra A Braunschweig Holger H Finze Maik M Ji Lei L Marder Todd B TB

Chemistry (Weinheim an der Bergstrasse, Germany) 20210503 31

Bis(1-(4-tolyl)-carboran-2-yl)-(4-tolyl)-borane [(1-(4-MeC6 H4 )-closo-1,2-C2 B10 H10 -2-)2 (4-MeC6 H4 )B] (1), a new bis(o-carboranyl)-(R)-borane was synthesised by lithiation of the o-carboranyl precursor and subsequent salt metathesis reaction with (4-tolyl)BBr2 . Cyclic voltammetry experiments on 1 show multiple distinct reduction events with a one-electron first reduction. In a selective reduc ...[more]

PMID: 33769625

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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 Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion.

Publications

Synthesis and Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion.

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