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Positional Isomerism in the N^N Ligand: How Much Difference Does a Methyl Group Make in [Cu(P^P)(N^N)]+ Complexes?

ABSTRACT: The synthesis and structural characterization of 5,6'-dimethyl-2,2'-bipyridine (5,6'-Me2bpy) are reported, along with the preparations and characterizations of [Cu(POP)(5,6'-Me2bpy)][PF6] and [Cu(xantphos)(5,6'-Me2bpy)][PF6] (POP = bis(2-(diphenylphosphanyl)phenyl)ether, xantphos = 4,5-bis(diphenylphosphanyl)-9,9-dimethyl-9H-xanthene). Single-crystal X-ray structure determinations of [Cu(POP)(5,6'-Me2bpy)][PF6] and [Cu(xantphos)(5,6'-Me2bpy)][PF6] confirmed distorted tetrahedral copper(I) coordination environments with the 5-methylpyridine ring of 5,6'-Me2bpy directed towards the (C6H4)2O unit of POP or the xanthene unit of xantphos. In the xantphos case, this preference may be attributed to C-H…π interactions involving both the 6-CH unit and the 5-methyl substituent in the 5-methylpyridine ring and the arene rings of the xanthene unit. 1H NMR spectroscopic data indicate that this ligand orientation is also preferred in solution. In solution and the solid state, [Cu(POP)(5,6'-Me2bpy)][PF6] and [Cu(xantphos)(5,6'-Me2bpy)][PF6] are yellow emitters, and, for powdered samples, photoluminescence quantum yields (PLQYs) are 12 and 11%, respectively, and excited-state lifetimes are 5 and 6 μs, respectively. These values are lower than PLQY and τ values for [Cu(POP)(6,6'-Me2bpy)][PF6] and [Cu(xantphos)(6,6'-Me2bpy)][PF6], and the investigation points to the 6,6'-dimethyl substitution pattern in the bpy ligand being critical for enhancement of the PLQY.

SUBMITTER: Brunner F

PROVIDER: S-EPMC7356218 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Positional Isomerism in the N^N Ligand: How Much Difference Does a Methyl Group Make in [Cu(P^P)(N^N)]+ Complexes?

Brunner Fabian F Prescimone Alessandro A Constable Edwin C EC Housecroft Catherine E CE

Molecules (Basel, Switzerland) 20200615 12

The synthesis and structural characterization of 5,6'-dimethyl-2,2'-bipyridine (5,6'-Me2bpy) are reported, along with the preparations and characterizations of [Cu(POP)(5,6'-Me2bpy)][PF6] and [Cu(xantphos)(5,6'-Me2bpy)][PF6] (POP = bis(2-(diphenylphosphanyl)phenyl)ether, xantphos = 4,5-bis(diphenylphosphanyl)-9,9-dimethyl-9H-xanthene). Single-crystal X-ray structure determinations of [Cu(POP)(5,6'-Me2bpy)][PF6] a ...[more]

PMID: 32549279

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Project description:Peptidomimetic antimicrobials exhibit a selective interaction with bacterial cells over mammalian cells once they have achieved an optimum amphiphilic balance (hydrophobicity/hydrophilicity) in the molecular architecture. To date, hydrophobicity and cationic charge have been considered the crucial parameters to attain such amphiphilic balance. However, optimization of these properties is not enough to circumvent unwanted toxicity towards mammalian cells. Hence, herein, we report new isoamphipathic antibacterial molecules (IAMs: 1-3) where positional isomerism was introduced as one of the guiding factors for molecular design. This class of molecules displayed good (MIC = 1-8 μg mL-1 or μM) to moderate [MIC = 32-64 μg mL-1 (32.2-64.4 μM)] antibacterial activity against multiple Gram-positive and Gram-negative bacteria. Positional isomerism showed a strong influence on regulating antibacterial activity and toxicity for ortho [IAM-1: MIC = 1-32 μg mL-1 (1-32.2 μM), HC50 = 650 μg mL-1 (654.6 μM)], meta [IAM-2: MIC = 1-16 μg mL-1 (1-16.1 μM), HC50 = 98 μg mL-1 (98.7 μM)] and para [IAM-3: MIC = 1-16 μg mL-1 (1-16.1 μM), HC50 = 160 μg mL-1 (161.1 μM)] isomers. Co-culture studies and investigation of membrane dynamics indicated that ortho isomer, IAM-1 exerted more selective activity towards bacterial over mammalian membranes, compared to meta and para isomers. Furthermore, the mechanism of action of the lead molecule (IAM-1) has been characterized through detailed molecular dynamics simulations. In addition, the lead molecule displayed substantial efficacy against dormant bacteria and mature biofilms, unlike conventional antibiotics. Importantly, IAM-1 exhibited moderate in vivo activity against MRSA wound infection in a murine model with no detectable dermal toxicity. Altogether, the report explored the design and development of isoamphipathic antibacterial molecules to establish the role of positional isomerism in achieving selective and potential antibacterial agents.

Dataset Information

Positional Isomerism in the N^N Ligand: How Much Difference Does a Methyl Group Make in [Cu(P^P)(N^N)]+ Complexes?

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Positional Isomerism in the N^N Ligand: How Much Difference Does a Methyl Group Make in [Cu(P^P)(N^N)]<sup>+</sup> Complexes?

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