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Assembly of Mn(III) Schiff Base Complexes with Heptacyanorhenate (IV)

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Assembly of Mn(III) Schiff Base Complexes with Heptacyanorhenate (IV) inorganics Article Assembly of Mn(III) Schiff Base Complexes with Heptacyanorhenate (IV) Taisiya S. Sukhikh 1,2 and Kira E. Vostrikova 1,* ID 1 Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia; [email protected] 2 Novosibirsk National Research State University, 630090 Novosibirsk, Russia * Correspondence: [email protected]; Tel.: +7-383-316-5831 Received: 8 August 2017; Accepted: 29 August 2017; Published: 1 September 2017 3− Abstract: A pioneering research on a self-assembly of the magneto-anisotropic module [Re(CN)7] with the Mn(III) complexes involving Salen type (N,N0-ethylenebis(salicylideneiminate)) Schiff 3MeO base (SB) ligands was performed using the known [Mn( Salen)(H2O)2]2(ClO4)2·H2O(1) and 5Me the firstly synthesized [Mn2( Salen)2OAc]PF6 (2). In the case of 1, a slow diffusion of the 3MeO component solutions led to the ionic compound Ph4P[Mn( Salen)(H2O)2]2[Re(CN)7]·6H2O(3). The direct mixing of the same solutions has resulted in the microcrystalline nearly insoluble 3MeO solid [Mn( Salen)(H2O))4Re(CN)7]ClO4·1.5MeCN·6.5H2O, which is likely to comprise the III + pentanuclear clusters [(Mn (SB)(H2O))4Re(CN)7] . The use of 2 resulted in a 2D-network 5Me assembly of octanuclear clusters, [{(Mn( Salen))6(H2O)2Re(CN)7}2Re(CN)7]Cl2(PF6)·H2O(4), incorporating one Re-center in a pentagonal bipyramid coordination environment, while another has strongly distorted capped trigonal prism as a coordination polyhedron. The latter was observed for the first time for Re(IV) complexes. A synthetic challenge to obtain the 0D 5Me assemblies with Re:Mn ≥ 3 has yielded a hexanuclear complex [Mn( Salen)H2O(i-PrOH)] 5Me [(Mn( Salen))5H2O(i-PrOH)2Re(CN)7](PF6)2(OAc)·2i-PrOH (5) being 1D chain via a bridging − phenoxyl group. Owing to a low solubility of the final product, an addition of a bulk anion Ph4B 3− to the MeCN/MeOH solution of [Re(CN)7] and 1 in ratio 1:6 resulted in rhenium-free matter 3MeO 3MeO [Mn( Salen)(H2O)2][Mn( Salen)(H2O)MeCN](Ph4B)2·5MeCN (6). Keywords: Mn(III) Schiff base complexes; heptacyanorhennate; Re(IV); salen type ligands 1. Introduction Complexes of Mn(III) with a quadridentate Schiff base (SB) ligand are widely used by chemists for applications in biology [1–4], catalysis [5–8], and molecular magnetism [9–15]. For a good reason, as many as eight Mn(III) ions of the twelve metallic centers are included in the first studied single-molecule magnet (SMM) Mn12O12(OA)16(H2O)4 [16,17]. Along with a high spin state, the {MnIII(SB)} magnetic modules possess uniaxial anisotropy upon completing their axial coordination positions during an assembly in heterometallic species. Why does this happen? Mn(III) ion in the high-spin state with S = 2 (3d4) is described by 5D ground term. In an 5 5 octahedral ligand field, the latter splits onto Eg and T2g levels. Jahn–Teller (JT) distortion lowers 5 5 the symmetry up to D4h (tetragonal geometry), which leads to an additional splitting of Eg into B1g 5 5 5 5 and A1g and of T2g into Eg and B2g (Scheme1). Note that if the complex has an axially-elongated 5 5 geometry (D4h), the ground term is B1g, while if the complex is compressed, A1g is the ground term. Further, the ground spin state degeneracy is removed by the second-order spin-orbit coupling 5 5 (SOC)—called zero-field splitting (ZFS) (Scheme1). Application of ZFS to B1g or A1g generates the lowest magnetization levels of Ms = ±2 or 0, with a gap of 4D between the ground spin state and the 5 5 highest excited level. When B1g is the ground term, D is negative, and conversely, when A1g is the Inorganics 2017, 5, 59; doi:10.3390/inorganics5030059 www.mdpi.com/journal/inorganics Inorganics 2017, 5, 59 2 of 16 Inorganics 2017, 5, 59 2 of 16 groundInorganics term, 2017, D5, 59is positive with a Hamiltonian of H = D(Sˆ2 − 1/3S(S + 1)) [9]. It was shown in [18]2 that of 16 III the anisotropy of thethe MnMnIII depends greatly on JT distortion. In In the case of axial elongation, the SB the anisotropy of the MnIII depends greatly on JT distortion. In the case of axial elongation, the SB complexes exhibit a negative ZFS D parameter with finitefinite uniaxialuniaxial anisotropyanisotropy [[19].19]. complexes exhibit a negative ZFS D parameter with finite uniaxial anisotropy [19]. 5B 5B2g 5T 2g 52g NN T2g NN 5 + Eg 5 Mn + Eg Mn 5D 5 O O D O O Free ion Free ion 5A X X 51g X X A1g 5 Ms NN Eg 5E Ms NN g 0 Mn+ 5 D 0 Mn+ Oh B1g D ±1 O 5B ±1 O O h 1g O O D4h 3D R R D4h 3D R R 5Me 2 ±2 5MeSalen – X = CH , R = 5-Me ±2 Salen – X = CH2, R = 5-Me ZFS 3MeOSalen – X = CH2, R = 3-OMe ZFS 3MeOSalen – X = CH2, R = 3-OMe (a) (b) (a) (b) Scheme 1. (a) Splitting of the 55D term by octahedral (Oh) and tetragonal (axial elongation, D4h) fields SchemeScheme 1. 1.( a()a Splitting) Splitting of of the the D5D term term by by octahedral octahedral (O (Oh)h) and and tetragonal tetragonal (axial (axial elongation, elongation, D D4h4h)) fields fields and by zero-field splitting; (b) Quadridentate environment of Mn(III) by Schiff base ligands: acacen andand by by zero-field zero-field splitting; splitting; ( b()b Quadridentate) Quadridentate environment environment of of Mn(III) Mn(III) by by Schiff Schiff base base ligands: ligands:acacen acacen (top) or salen (N,N0′-ethylene-bis(salicylideneiminate) (bottom), see text. (top)(top) or orsalen salen(N (N,N,N-ethylene-bis(salicylideneiminate)′-ethylene-bis(salicylideneiminate) (bottom), (bottom), see see text. text. Thus, the MnIII in the square planar {NNOO} coordination environment of the SB ligand Thus,Thus, thethe MnMnIIIIII inin thethe squaresquare planarplanar {NNOO}{NNOO} coordinationcoordination environmentenvironment ofof thethe SBSB ligandligand (Scheme 2) is an excellent building block for the construction of extended and molecular magnetic (Scheme(Scheme2 )2) is is an an excellent excellent building building block block for for the the construction construction of of extended extended and and molecular molecular magnetic magnetic assemblies, because it possesses potentially vacant axial positions to bind heterometallic complex by assemblies,assemblies, becausebecause itit possessespossesses potentially vacant vacant axial axial positions positions to to bind bind heterometallic heterometallic complex complex by means of ambidentate ligands. As a result of such coordination, a uniaxial magnetic anisotropy bymeans means of of ambidentate ambidentate ligands. ligands. As As a aresult result of of such coordination,coordination, aa uniaxialuniaxial magneticmagnetic anisotropyanisotropy appears along the line of joint. Moreover, a wide variation of the SB ligand structure by means of the appearsappears along along thethe lineline ofof joint. Moreover, Moreover, a a wide wide variation variation of of the the SB SB ligand ligand structure structure by by means means of ofthe introduction of various substituents contributes to fine tailoring of target material organization, theintroduction introduction of ofvarious various substituents substituents contributes contributes to to fine fine tailoring tailoring of targettarget materialmaterial organization,organization, which is very important for the tuning of magnetic properties. Besides, it is sometimes necessary to whichwhich is is very very important important for for the the tuning tuning of of magnetic magnetic properties. properties. Besides, Besides, it it is is sometimes sometimes necessary necessary to to take into consideration not only the choice of SB ligand but also the complete parameters of the taketake into into consideration consideration not not only only the the choice choice of SB of ligand SB ligand but also but the also complete the complete parameters parameters of the Mn(III) of the Mn(III) precursor based on it. For example, it is essential to consider the presence or absence of precursorMn(III) precursor based on it.based For example,on it. For it example, is essential it tois consideressential theto consider presence orthe absence presence of dimerizationor absence of dimerization in the manganese complex, as well as carefully select the counterions compensating the indimerization the manganese in the complex, manganese as well comp as carefullylex, as well select as carefully the counterions select the compensating counterions the compensating charge in both the charge in both the starting materials and in the final products. thecharge starting in both materials the starting and in materials the final products.and in the final products. [Mn(3MeOSalen)H O) Re(CN) ]ClO ·1.5MeCN·6.5H O [Mn(3MeOSalen)H2 O)4 Re(CN)7 ]ClO4 ·1.5MeCN·6.5H2 O [Mn(3MeOSalen)(H O) ] (ClO ) ·2H O, 1 Ph PCl 2 4 7 4 2 [Mn(3MeOSalen)(H2 O)2 2] (ClO4 2) ·2H2 O, 1 Ph4 PCl Ph P[Mn(3MeOSalen)(H O) ] [Re(CN) ]·6H O, 3 + (n-Bu N)2 [Re(CN)2 2 4] 2 2 4 Ph4 P[Mn(3MeOSalen)(H2 O)2 2] [Re(CN)7 ]·6H2 O, 3 + (n-Bu4 N)3 [Re(CN)7 ] 4 2 2 2 7 2 4 3 7 NaBPh 3MeO 3MeO NaBPh4 [Mn( 3MeOSalen)(H2O)2][Mn( 3MeOSalen)(H2O)MeCN] 4 [Mn( Salen)(H2O)2][Mn( Salen)(H2O)MeCN] (Ph4B)2·5CH3CN, 6 (Ph4B)2·5CH3CN, 6 PPNCl 5Me PPNCl [{(Mn( 5MeSalen))6(H2O)2Re(CN)7}2Re(CN)7] [Mn (5MeSalen) OAc]PF , 2 [{(Mn( Salen))6(H2O)2Re(CN)7}2Re(CN)7] 2 5Me 2 6 Cl2(PF6)·H2O, 4 [Mn2( Salen)2OAc]PF6, 2 Cl (PF )·H O, 4 + (n-Bu N) [Re(CN) ] 2 5Me6 2 5Me 4 3 7 NH4PF6 [Mn( Salen)(H O)i-PrOH][(Mn( Salen)) H O + (n-Bu4N)3[Re(CN)7] NH PF 5Me 2 5Me 5 2 4 6 [Mn( Salen)(H2O)i-PrOH][(Mn( Salen))5H2O (i-PrOH)2Re(CN)7](PF6)2·H2O·5i-PrOH, 5 (i-PrOH)2Re(CN)7](PF6)2·H2O·5i-PrOH, 5 Scheme 2.
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