We report the synthesis of a new phenalenyl ligand, functionalized with a methyl ester electron withdrawing group, named 9-hydroxy-1-oxo-1H-phenalen-5-methyl carboxylate (L) and the generated complexes [Ru(bpy)2L]PF6 and [(η 6 -C6H6)Ru(L)Cl]. Compounds were characterized by spectroscopic and X-ray diffraction methods and their electrochemical behavior was investigated via cyclic voltammetry and UV-vis spectroelectrochemistry. The one-electron oxidized compounds have unpaired electron located in the phenalenyl ring, as supported by theoretical calculations (DFT) and EPR results. Langmuir-Blodgett (LB) films deposited by [Ru(bpy)2L] 2+/3+ species mixed with stearic acid are electroactive, showing quasi-reversible
Herein we describe the synthesis, structural, spectroscopic and magnetic characterization of a new pentacoordinated bicopper(II) complex containing 2‐formylpyridine semicarbazone (HSCpy), referred as complex 1. Each copper core is bound to one N,N,O‐tridentate HSCpy ligand and connected to the second metal ion by two μ‐oxygen sulfato‐bridges. The compound shows an extensive association between the neutral complex molecule and water as crystallization solvate through classical N−H⋅⋅⋅O, O−H⋅⋅⋅O and, non‐classical C−H⋅⋅⋅O intermolecular hydrogen bonding generating a supramolecular 3‐D assembly in the solid state. Jahn‐Teller stabilization energies at 5144 cm−1 and spin orbit coupling constants λ=−442 cm−1 were estimated using the electronic spectra and Electron Paramagnetic Resonance data. The variable‐temperature (2‐300 K) magnetic measurements showed isotropic magnetic interaction between the two copper ions, according to the spin Hamiltonian yielding 2 J values at −0.34 cm−1 for complex 1, in accordance with a very small antiferromagnetic interaction between copper ions kept apart by 3.24 Å. The results are compared to the thiosemicarbazone analogue.
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