A series of homo- and heterotrinuclear complexes containing three face-sharing octahedra has been synthesized by using the pendent arm macrocyclic ligands 1,4,7-tris(3,5-dimethyl-2-hydroxybenzyl)-1,4,7-triazacyclononane, L0H3, and 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane, LH3: [{L0NiII}2NiII] (1) and [{LCoIII}2CoIII](PF6)3 (2); [{LCoIII}2Ni] n + (n = 2 (3), 3 (4), 4 (5)); [{LNi}2CoIII] n + (n = 1 (6), 2 (7), 3 (8)) and its linkage isomers [{LNi}Ni{CoIIIL}] n + (n = 1 (9), 2 (10), 3 (11)) and, finally, the complexes [{LNi}2Ni] n + (n = 0 (12), 1 (13), 2 (14), 3 (15)). In complex 1 three octahedral NiII ions form a linear array with two terminal [L0NiII]- moieties in a facial N3O3 donor set and a central NiII ion which is connected to the terminal ions via six phenolate bridging pendent arms of L0. In complexes 2−15 the three metal ions are always in the same ligand matrix yielding an N3M(μ-S)3M(μ-S)3MN3 first-coordination sphere regardless of the nature of the metal ions (nickel or cobalt) or their formal oxidation states. From temperature dependent magnetic susceptibility measurements it has been determined that 1 has an S = 3 ground state whereas in 12 it is S = 1. In order to understand this difference in exchange coupling (ferromagnetic in 1 and antiferromagnetic in 12) in two apparently very similar complexes the magnetic properties of 2−15 have been investigated. Complex 3 has an S = 1 and 4 an S = 1/2, and 5 is diamagnetic (S = 0) as is its isoelectronic counterpart 2. This indicates the availability of the oxidation states II, III, and IV of the central NiS6 unit. In the isostructural complexes 6, 7, and 8, two terminal nickel ions are bridged by a central diamagnetic CoIII. The exchange coupling between two terminal paramagnetic nickel ions was studied as a function of their formal oxidation state. In 6 the two NiII ions are ferromagnetically coupled (S = 2); the mixed-valent NiIINiIII species 7 has an S = 3/2 ground state and in 8 most probably two NiIII ions (d7 low spin) give rise to an S = 1 ground state. In contrast, in the series 9, 10, and 11 where two nickel ions are in a position adjacent to each other 9 has an S = 0 (antiferromagnetic coupling), but in the mixed-valent complex 10 an S = 3/2 ground state (ferromagnetic coupling) is observed. In 11 an S = 1 ground state prevails which may be achieved by ferromagnetic coupling between two NiIII ions. For the trinuclear nickel complexes 12−15 an S = 1 ground state has been determined for 12, an S = 3/2 for the mixed valent complex 13, and an S = 2 for 14, and 15 exhibits an S = 3/2 ground state. The Goodenough−Kanamori rules do not provide a consistent explanation for the observed ground states in all cases. The concept of double exchange, originally introduced by Zener in 1951, appears to provide a more appropriate description for the mixed-valent species 7, 10, 13, 14, and 15. This picture is corroborated by the electrochemistry and EPR spectroscopy of complexes.
The hexadentate, pendant arm macrocycle 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (H(3)L) has been synthesized and isolated as its trihydrochloride, H(3)L.3HCl, or sodium salt, Na(3)L, and its coordination chemistry with first-row transition metals has been studied. Mononuclear complexes of the type [LM(III)] (M = Ga (1), In (2), V (3), Cr (4), Mn (5), Fe,Co (6)) have been isolated as have the one-electron-oxidized forms [LM]PF(6) (M = V(IV) (3a), Mn(IV) (5a)). The crystal structure of 6 has been determined by single-crystal X-ray crystallography. Complex 6 crystallizes in the orthorhombic space group Iba2, with cell constants a = 14.206(8) Å, b = 22.53(1) Å, c = 26.07(1) Å, V = 8344.0(3) Å(3), and Z = 8. The cobalt(III) ion is in a distorted octahedral fac-N(3)S(3) donor set. The reaction of L with divalent metal chlorides in a 1:2 ratio in methanol affords the homodinuclear complexes [LM(II)(2)Cl] (M = Mn (7), Co (8), Ni (9), Zn (10), Cd (11)) where one metal is six- (N(3)MS(3)) and the other is four-coordinate (S(3)MCl); the two polyhedra are linked by three &mgr;(2)-thiolato bridges. Heterodinuclear complexes of the type [LM(1)M(2)Cl] have been obtained from [LM(2)Cl] species by abstraction of the four-coordinate metal ion and replacement by a different metal ion. The complexes [LZn(II)M(II)Cl] (M = Fe (12), Co (13), Ni (14)), [LNi(II)M(II)Cl] (M = Co (15), Zn (16)), and [LMn(II)M(II)Cl] (M = Fe (17), Co (18), Ni (19), Zn (20), Cd (21), Hg (22)) have been isolated as solid materials. The crystal structure of 14 has been determined by X-ray crystallography. Complex 14 crystallizes in the orthorhombic space group P2(1)2(1)2(1), with cell constants a = 15.45(1) Å, b = 17.77(1) Å, c = 17.58(1) Å, V = 4826.5(4) Å(3), and Z = 4. The linkage isomers 14 and 16 show characteristic electronic spectra for octahedrally and tetrahedrally coordinated Ni(II), respectively. The electronic structures of new complexes have been investigated by UV-vis spectroscopy; their magnetochemistry and electrochemistry are reported.
The reaction of mononuclear [LFe(III)] where L represents the trianionic ligand 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane with NiCl(2).6H(2)O and subsequent oxidations with [Ni(III)(tacn)(2)](ClO(4))(3) (tacn = 1,4,7-triazacyclononane) and PbO(2)/methanesulfonic acid produced an isostructural series of complexes [LFeNiFeL](n)()(+) (n = 2 (1), n = 3 (2), n = 4 (3)), which were isolated as PF(6)(-) (1, 3) or ClO(4)(-) salts (2). The molecular structures were established by X-ray crystallography for [LFeNiFeL](ClO(4))(2).5CH(3)CN (1), C(88)H(123)Cl(2)Fe(2)N(11)NiO(8)S(6), and [LFeNiFeL](ClO(4))(3).8acetone (2), C(102)H(156)Cl(3)Fe(2)N(6)NiO(20)S(6). Both compounds crystallize in the triclinic space group P&onemacr; with a = 13.065(2) Å (13.155(2) Å), b = 13.626(3) Å (13.747(3) Å), c = 14.043(3) Å (16.237(3) Å), alpha = 114.47(3) degrees (114.20(2) degrees ), beta = 97.67(3) degrees (96.57(2) degrees ), gamma = 90.34(3) degrees (98.86(2) degrees ), Z = 1(1) (values in parentheses refer to 2). The cations in 1, 2, and 3 have been determined to be isostructural by Fe and Ni K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. All compounds contain linear trinuclear cations (face-sharing octahedral) with an N(3)Fe(&mgr;-SR)(3)Ni(&mgr;-SR)(3)FeN(3) core structure. The electronic structures of 1, 2, and 3 have been studied by Fe and Ni K-edge X-ray absorption near edge (XANES), UV-vis, EPR, and Mössbauer spectroscopy as well as by temperature-dependent magnetic susceptibility measurements. Complexes 1 and 3 possess an S(t)() = 0 whereas 2 has an S(t)() = (1)/(2) ground state. It is shown that the electronic structures cannot be described by using localized valences (oxidation states). Delocalized models invoking the double-exchange mechanism are appropriate; i.e., spin-dependent delocalization via a double-exchange mechanism yields the correct ground state in each case. 1, 2, and 3 represent the first examples where double exchange stabilizes a ground state of minimum spin multiplicity.
The trinuclear complexes [LNaMlvNaL] (M = Ru 1, 0 s 2) where L represents the hexadentate ligand 1,4,7-tris(4-tertbutyl-2-mercaptobenzyl)-l,4,7-triazacyclononane have been synthesized and 1 has been characterized by X-ray crystallography; complex 1 contains an octahedral M'VS6 central core and two trigonal-prismatic terminal LNa units with an N3S3 donor set; the electronic structure of the MlvSs core (M = Ru, Os), has been established as S = 1 by temperature-dependent magnetic susceptibility measurements.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.