Heterobridged dinuclear, tetranuclear, dinuclear-based 1-D, and heptanuclear-based 1-D complexes of copper(II) derived from a dinucleating ligand: Syntheses, structures, magnetochemistry, spectroscopy, and catecholase activity

摘要

The work in this paper presents syntheses, characterization, crystal structures, variable-temperature/field magnetic properties, catecholase activity, and electrospray ionization mass spectroscopic (ESI-MS positive) study of five copper(II) complexes of composition [Cu~(II)_2L(μ_(1,1)-NO_3)(H_ 2O)(NO _3)](NO_3) (1), [{Cu~(II)_2L(μ-OH) (H_2O)}(μ-ClO_4)]n(ClO_4) n (2), [{Cu~(II)_2L(NCS)_2}(μ _(1,3)-NCS)]n (3), [{Cu~(II)_2L(μ _(1,1)-N_3)(ClO_4)}_2(μ _(1,3)-N_3)_2] (4), and [{Cu~(II)_2L(μ-OH)}{Cu~(II)_2L(μ_(1,1)-N _3)}{Cu~(II)(μ_(1,1)-N_3) _4(dmf)}{Cu~(II)_2(μ_(1,1)-N _3)_2(N_3)_4}]n?ndmf (5), derived from a new compartmental ligand 2,6-bis[N-(2-pyridylethyl) formidoyl]-4-ethylphenol, which is the 1:2 condensation product of 4-ethyl-2,6-diformylphenol and 2-(2-aminoethyl)pyridine. The title compounds are either of the following nuclearities/topologies: dinuclear (1), dinuclear-based one-dimensional (2 and 3), tetranuclear (4), and heptanuclear-based one-dimensional (5). The bridging moieties in 1-5 are as follows: μ-phenoxo-μ_(1,1)-nitrate (1), μ-phenoxo-μ-hydroxo and μ-perchlorate (2), μ-phenoxo and μ_(1,3)-thiocyanate (3), μ-phenoxo-μ_(1,1)-azide and μ_(1,3)-azide (4), μ-phenoxo-μ-hydroxo, μ-phenoxo-μ_(1,1)-azide, and μ_(1,1)-azide (5). All the five compounds exhibit overall antiferromagnetic interaction. The J values in 1-4 have been determined (-135 cm~(-1) for 1, -298 cm~(-1) for 2, -105 cm~(-1) for 3, -119.5 cm~(-1) for 4). The pairwise interactions in 5 have been evaluated qualitatively to result in S_T = 3/2 spin ground state, which has been verified by magnetization experiment. Utilizing 3,5-di-tert-butyl catechol (3,5-DTBCH_2) as the substrate, catecholase activity of all the five complexes have been checked. While 1 and 3 are inactive, complexes 2, 4, and 5 show catecholase activity with turn over numbers 39 h~(-1) (for 2), 40 h~(-1) (for 4), and 48 h~(-1) (for 5) in dmf and 167 h~(-1) (for 2) and 215 h~(-1) (for 4) in acetonitrile. Conductance of the dmf solution of the complexes has been measured, revealing that bridging moieties and nuclearity have been almost retained in solution. Electrospray ionization mass (ESI-MS positive) spectra of complexes 1, 2, and 4 have been recorded in acetonitrile solutions and the positive ions have been well characterized. ESI-MS positive spectrum of complex 2 in presence of 3,5-DTBCH2 have also been recorded and, interestingly, a positive ion [Cu~(II)_2L(μ-3,5-DTBC~(2-))(3,5-DTBCH ~-)Na~I]~+ has been identified.