Designing a Redox Noninnocent Phenalenyl-Based Copper(II) Complex: An Autotandem Catalyst for the Selective Oxidation of Polycyclic Aromatic Hydrocarbons (PAHs)

Abstract

A square-planar [Cu II L] complex 1, based on the redox-active phenalenyl unit LH 2 = 9,9′-(ethane-1,2diylbis(azanediyl))bis(1H-phenalen-1-one), is prepared and structurally characterized by single-crystal X-ray diffraction analysis. Complex 1 crystallizes at room temperature with the P1 space group. The molecular structure of 1 reveals the presence of intriguing C−H•••Cu intermolecular anagostic interactions of the order ∼2.7715 Å. Utilizing the presence of anagostic interactions and the free nonbonding molecular orbitals (NBMOs) of the closed-shell phenalenyl unit in 1, the oxidation reactions of some industrially important polycyclic aromatic hydrocarbons (PAHs) in the presence of the [Cu II L] complex under very mild conditions have been reported. The direct conversion of anthracene-9-carbaldehyde to 9,10-anthraquinone in one step concludes that the catalyst shows dual activity in the chemical transformations. This also includes the first report of a "single-step" catalytic transformation of pyrene-1carbaldehyde to the synthetically difficult pyren-4-ol, a precursor for the synthesis of several novel fluorescent probes for cell imaging.

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H2O2 fuel cell

“…22 Raman et al explored a Zn( ii ) complex containing closed-shell PLY to fabricate a spin-memory device. 23 The coordination of PLY with the first-row transition metals, such as Cr( iii ), 24 Mn( iii )/Mn( ii ), 19,25 Fe( iii ), 21 Co( ii ), 26,27 Ni( ii ), 20 Cu( ii ), 28 etc. , prevents the occurrence of unfavorable oxidation states in the central metal ions during the homogeneous catalytic cycles.…”

Redox Switching Behavior in Resistive Memory Device Designed Using a Solution-Processable Phenalenyl-Based Co(II) Complex: Experimental and DFT Studies

“…TMCs derived from electro-active phenalenyl-based ligands are well-known in the literature. − Haddon, in 1975, introduced the importance of the phenalenyl (PLY) molecule in the modern semiconductor industry and regarded PLY as one of the graphene fragments . The past studies have made it evident that the delocalized carbon-based charged species with unpaired spin in the PLY redox motif have exhibited many promising molecular device properties. − Raman et al used the zinc­(II) metal ion complex containing a cationic PLY unit as an electro-active material for constructing a spin-based memory device .…”

A Catecholaldimine-Based NiII-Complex as an Effective Catalyst for the Direct Conversion of Alcohols to trans-Cinnamonitriles and Aldehydes

“…Because of our ongoing interest in redox-active ligand-based metal complexes for catalytic selective oxidations 24 and being inspired by the catalytic activity of Ni-complexes, 25,26 With the catalyst in hand, we became interested in exploring the synthesis of β-substituted acrylonitriles in a single step in an inexpensive and environmentally friendly way. In the presence of [Ni(HL) 2 ] 1 catalyst (1.0 mol %), a series of studies were conducted for oxidative olefination using 4methoxybenzyl alcohol and acetonitrile as model substrates with varying bases and reaction conditions (Table 1).…”

“…Because of our ongoing interest in redox-active ligand-based metal complexes for catalytic selective oxidations and being inspired by the catalytic activity of Ni-complexes, , we became interested in assessing the efficacy of newly designed Ni-complex [Ni­(HL) 2 ] 1 as a catalyst to develop the oxidative olefination of alcohols with acetonitrile in a one-pot manner. Herein, we introduced a new N, N, and O-type catecholaldimine ligand and its nickel complex [Ni­(HL) 2 ] 1 .…”