title: Structural and magnetic properties of semiquinonate based Al(iii) and Ga(iii) complexes.
abstract: The reaction of anhydrous MCl3(M = Al(iii) or Ga(iii)) with one-electron-reduced 3,5-di-tert-butyl-1,2-ortho-benzoquinone (using metallic sodium) led us to isolate two distinct metal complexes of Al(iii) and Ga(iii), which were structurally and magnetically characterized. Complex 1 crystallized in the monoclinic P21/n space group, whereas 2 crystallized in the triclinic P1[combining macron] space group. Interestingly, whereas the Al(iii) derivative was obtained as a dimer with the molecular formula [Al2(μ-HL-)2(L˙-)4] (1) (where L˙-is a semiquinonate radical and HL-is a monoanionic catecholate ligand), the Ga(iii) derivative crystallized as [Ga(L˙-)3] (2), which is a polymorph of a previously reported complex. The presence of both catecholate and/or semiquinonate ligands in 1 and 2 was confirmed by single-crystal X-ray diffraction, mass spectrometry, and NMR and infrared spectroscopy techniques. The crystalline phase purity of the complexes was confirmed by powder X-ray diffraction (PXRD). Measurements of direct-current magnetic susceptibility, which were performed on a polycrystalline samples, revealed that in both complexes the semiquinonate radical anions are coupled ferromagnetically via the diamagnetic metal ion. The magnetism data of both complexes were modelled using the Heisenberg-Van Vleck-Dirac (HDVV) Hamiltonian, and the extracted parameters are consistent with the literature reports. The details of the electronic structures of the ground states of 1 and 2 were further investigated via X-band (ca. 9 GHz) electron paramagnetic resonance (EPR). The EPR spectrum of 2 could be reproduced by considering a quartet ground state with zero-field splitting and hyperfine coupling, whereas attempts to simulate all the EPR spectral features observed in a frozen solution of 1 by assuming it was a pure phase failed. A correct simulation required the simultaneous inclusion of contributions from a quartet and a triplet state. This evidently suggests that the dimeric complex of 1 is in equilibrium with a monomeric [Al(L˙-)3] complex in solution.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra-400076, India. eswar@chem.iitb.ac.in.
authors.forename: Chinmoy
authors.initials: C
authors.lastname: Das
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra-400076, India. eswar@chem.iitb.ac.in.
authors.forename: Pragya
authors.initials: P
authors.lastname: Shukla
authors.affiliation: Dipartimento di Chimica "U. Schiff" and UdR INSTM, Università degli Studi di Firenze, Via della Lastruccia 3, 50019 Sesto Fiorentino, Italy.
authors.forename: Lorenzo
authors.identifier: http://orcid.org/0000-0003-4785-1331
authors.initials: L
authors.lastname: Sorace
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra-400076, India. eswar@chem.iitb.ac.in.
authors.forename: Maheswaran
authors.initials: M
authors.lastname: Shanmugam