[Show abstract][Hide abstract] ABSTRACT: The copper(II) complexes of protonated pentadentate Schiff-base ligands with [Cu(H(2)L(n))](ClO(4))(2) formula (n = 3-6, 3-6) have been synthesized and characterized (H(2)L(3) = N-((2-methylimidazol-4-yl)methylene)-3-aminpropyl-N'-((2-methylimidazol-4-yl)methylene)-4'-aminobutylamine, H(2)L(4) = N-((2-phenylimidazol-4-yl)methylene)-3-aminpropyl-N'-((2-phenyl-imidazol-4-yl)methylene)-4'-aminobutylamine, H(2)L(5) = N,N'-bis((2-phenylimidazol-4-yl)methylene)-3,3'-diaminodipropylmethylamine, H(2)L(6) = N-((2-methylimidazol-4-yl)methylene)-2-aminoethyl-N'-((2-methylimidazol-4-yl)methylene)-3'-aminopropylamine. The mono-deprotonated complexes 3', 4', and 5' contain one imidazole and one imidazolate groups per unit and are Delta (clockwise) or Lambda (anticlockwise) enantiomorphs due to the spiral arrangement of the ligand around copper(II) ion. They function as chiral building components for a self-assembly process resulting from the formation of hydrogen bonds between the imidazole and imidazolate groups of adjacent units to yield 1D zigzag-chain structures. The distance between hydrogen-bonded nitrogen atoms is 2.81(2), 2.832(9), and 2.875(9) Å for 3', 4', and 5', respectively. The crystal lattice of 3' yielded either.DeltaDeltaDelta. or.LambdaLambdaLambda. isotactic 1D zigzag-chains, while the crystal lattices of 4' and 5' yielded.DeltaLambdaDeltaLambda. syndiotactic 1D zigzag-chains. In 3', two adjacent methyl groups at the 2-position connected by hydrogen bond array in the same direction, thus allowing homochiral aggregation of the complex molecules in a 1D chain. On the other hand, in 4' and 5', two adjacent bulky phenyl groups require opposite orientations, thus allowing heterochiral aggregation. Enantioselective aggregation with homochirality or heterochirality can thus be controlled with suitable substituents. While its mononuclear precursor 6 is pentacoordinated with the N(5) donor set of the pentadentate ligand H(2)L(6), the deprotonated complex 6' has an imidazolate-bridged tetranuclear cyclic structure with a Cu-Cu distance of 6.086(2) Å. The ligand in 6' is tetradentate and includes an hexahydropyrimidine ring resulting from a deprotonation induced rearrangement reaction.
No preview · Article · Aug 1999 · Inorganic Chemistry
[Show abstract][Hide abstract] ABSTRACT: The monomer <--> oligomer interconversion of the reported metal complexes is generated by proton abstraction/supply as a common external information input. The mononuclear copper(II) complexes 1 and 2 with [CuCl(2)(HL(n)())] chemical formula have been prepared (HL(1) = N-(2-methylimidazol-4-ylmethylidene)-2-aminoethylpyridine; HL(2) = N-(2-phenylimidazol-4-ylmethylidene)-2-aminoethylpyridine). The crystal structures were determined. 1.H(2)O, C(12)H(16)N(4)OCl(2)Cu: a = 13.773(2) Å, b = 8.245(2) Å, c = 13.861(2) Å, beta = 110.10(1) degrees, monoclinic, P2(1)/n, and Z = 4. 2, C(17)H(16)N(4)Cl(2)Cu: a = 7.6659(7) Å, b = 16.287(1) Å, c = 14.103(1) Å, beta = 95.058(7) degrees, monoclinic, P2(1)/c, and Z = 4. Complexes 1.H(2)O and 2 assume a pentacoordinated square pyramidal geometry with a N(3)Cl(2) donor set consisting of the nitrogen atoms of the protonated tridentate ligand and two chloride ions in the solid state, while in aqueous solution the Cu(II) ion is tetracoordinated (N(3)Ow donor set). When 1 and 2 are treated with an equimolar amount of sodium hydroxide or triethylamine, the deprotonation of the imidazole moiety promotes a self-assembly process, arising from coordination of the imidazolate nitrogen atom to a Cu(II) ion of an adjacent unit, to yield compounds 1'.4H(2)O as the perchlorate salt, and 2'a.6H(2)O as the perchlorate salt and( )()2'b as the hexafluorophosphate salt, respectively. 1'.4H(2)O, C(12)H(15)N(4)O(5)ClCu: a = b = 13.966(2) Å, c = 33.689(3) Å, tetragonal, I4(1)/a, and Z = 16. 2'a.6H(2)O, C(51)H(51)N(12)O(15)Cl(3)Cu(3): a = 15.177(3) Å, b = 15.747(3) Å, c = 14.128(3) Å, alpha = 100.06(2) degrees, beta = 110.37(2) degrees, gamma = 63.54(1) degrees, triclinic, P&onemacr;, and Z = 2. 2'b, C(17)H(15)N(9)F(6)PCu: a = b = 29.812(5) Å, c = 11.484(3) Å, trigonal, R&thremacr;, and Z = 18. The nuclearity of the self-assembled molecules and their detailed structure were confirmed to be cyclic imidazolate-bridged tetranuclear for 1'.4H(2)O and hexanuclear for 2'a.6H(2)O and 2'b, respectively, through single-crystal X-ray analyses and FAB-MS spectra. Variable-temperature experimental magnetic susceptibility data were well reproduced by using the Heisenberg model based on a cyclic tetranuclear structure for 1' and a cyclic hexanuclear structure for 2'a and 2'b. The reversible interconversion between the protonated monomeric and deprotonated oligomeric species were confirmed by pH-dependent potentiometric and electronic spectral titrations in aqueous solution, whereas the Pd(II) complex did not show a perfect disassembly process.
No preview · Article · Apr 1999 · Inorganic Chemistry
[Show abstract][Hide abstract] ABSTRACT: The manganese(III) complex K[MnL(py)(2)].py (H(4)L = 1,2-bis(2-hydroxybenzamido)benzene, py = pyridine) reacted as a ligand complex at the two phenoxo oxygen atoms with metal(II) ion and 2,2'-bipyridine to give a series of heterometal complexes [Mn(MeOH)L(OH)M(bpy)](2) (M(II) = Zn (1); Cu (2); Ni (3); Mn (4)). X-ray structures were determined 1, C(68)H(74)N(8)O(18)Mn(2)Zn(2): a = 12.367(3) Å, b = 12.844(2) Å, c = 12.262(2) Å, alpha = 106.58(1) degrees, beta = 117.89(1) degrees, gamma = 78.57(2) degrees, triclinic, P&onemacr;, and Z = 1. 2, C(68)H(74)N(8)O(18)Mn(2)Cu(2): a = 13.447(1) Å, b = 12.670(2) Å, c = 21.732(1) Å, beta = 107.076(5) degrees, monoclinic, P2(1)/n, and Z =2. 3, C(68)H(74)N(8)O(18)Mn(2)Ni(2): a = 12.358(3) Å, b = 12.847(3) Å, c = 12.315(3) Å, alpha = 106.63(2) degrees, beta = 118.71(1) degrees, gamma = 78.32(2) degrees, triclinic, P&onemacr;, and Z = 1. 4, C(66)H(66)N(8)O(16)Mn(4): a = 12.511(2) Å, b = 21.129(3) Å, c = 12.811(1) Å, beta = 110.12(1) degrees, monoclinic, P2(1)/n, and Z = 2. The X-ray analyses confirmed that each of the crystals consists of an incomplete double-cubane molecule with a [Mn(2)M(2)O(6)] core, in which two M(II) ions are bridged by two hydroxo groups to form a planar dinuclear moiety bridged by di-&mgr;-hydroxo groups [(bpy)M(OH)(2)M(bpy)](2+) and the dinuclear moiety is sandwiched between two Mn(III) complexes [Mn(MeOH)L](-). The Mn(III) ion and the dinuclear M(II) moiety are triply bridged by the one hydroxo oxygen of the dinuclear moiety and two phenoxo oxygen atoms of the Mn(III) ligand complex. The two phenoxo oxygen atoms of the Mn(III) ligand complex coordinate as an axial ligand to two independent metal(II) ions of the dinuclear moiety. The magnetic susceptibilities of 1-4 were measured in the temperature range of 2-300 K. All the Mn(III) ions in these complexes are in a high-spin state of S(Mn) = 2 with a d(4) electronic configuration, and the metal(II) ions are in the spin states of S(Zn) = 0, S(Cu) = 1/2, S(Ni) = 1, and S(Mn(II)) = 1/2 (low-spin). The magnetic susceptibility data are well reproduced by the following spin Hamiltonian based on the rhombus spin coupling model with spin (S(1), S(2), S(3), S(4)) = (2, S(M), 2, S(M)), including a zero-field splitting term for the Mn(III) centers: H = g(Mn)beta(S(1) + S(3)).H + g(M)beta(S(2) + S(4)).H - 2J(S(1).S(2) + S(2).S(3) + S(3).S(4) + S(4).S(1)) - 2J'(S(2).S(4)) + D(Mn)[S(1z)(2) + S(3z)(2)], in which g(Mn) and g(M) are the g factors of the Mn(III) and M(II) ions, J and J' are the Mn(III)-M(II) and M(II)-M(II) Heisenberg coupling constants, and D is the zero-field splitting parameter of Mn(III). The calculated best-fit parameters are as follows: g(Mn) = 1.91, g(Cu) = 2.39, J = -4.5 cm(-)(1), J' = -8.1 cm(-)(1), and D(Mn) = -4.9 cm(-)(1) for 2; g(Mn) = 1.97, g(Ni) = 2.23, J = -1.5 cm(-)(1), J' = -2.6 cm(-)(1), and D(Mn) = -5.5 cm(-)(1) for 3; and g(Mn) =1.95, g(Mn(II)) = 2.29, J = -3.5 cm(-)(1), J' = -14.1 cm(-)(1), and D(Mn) = -12.0 cm(-)(1) for 4. The spin frustration due to the incomplete double-cubane structure is discussed.
No preview · Article · Nov 1998 · Inorganic Chemistry
[Show abstract][Hide abstract] ABSTRACT: Two copper(II) complexes with N,N'-bis(2-substituted-imidazol-4-ylmethylidene)-1,4-diaminobutane (2-substituent = H, 1; Me, 2) were synthesized, and their deprotonation assembly behavior was studied. X-ray analyses of 1 and 2 revealed that the molecules assume a butterfly shape bent by a line of N(2)-Cu-N(4) where the angle of N(3)-Cu-N(5) representing the extent of the molecular bend is 150.9(2) degrees and 105.66(8) degrees for 1 and 2, respectively. Due to the molecular bend, two imidazole moieties (sites A and B) are recognized as two inequivalent groups for the deprotonation process in which the imidazole group of site A is in an equatorial CuN(3) plane, while that of site B is in a CuN(2) plane bent from the equatorial coordination plane. 1 dissociates a proton of site B first to give an infinite zigzag-chain compound 1', while 2 dissociates a proton of site A first to give a cyclic-tetranuclear compound 2'. 2' undergoes a further deprotonation to give an electrically neutral di-deprotonated complex 2". The interconversion between the protonated monomer and the deprotonated oligomer/polymer was investigated by pH-dependent potentiometric and absorption spectrometric titrations.
No preview · Article · Aug 1998 · Inorganic Chemistry
[Show abstract][Hide abstract] ABSTRACT: Protonated and deprotonated forms of nickel(II) complex with N-salicylidene-N'-(2-phenylimidazol-4-ylmethylidene)-1,3-propanediamine, 1 and 1′, were synthesized and characterized. The X-ray crystal structures of 1-H2O and 1′ were determined: 1-H2O, P21/n (No. 14), a= 11.642(2), b= 12.908(3), c = 15.264(2) Å, β = 96.642(1)°; 1′, I41,/a (No. 88), a = 22.651(3), c = 13.950(7) Å. The crystal of 1-H2O assumes a dinuclear structure bridged by the di-μ-phenoxo moiety in an out-of-plane fashion with Ni-Ni = 3.173(1) Å and Ni-O = 2.126(3) Å of the Ni2O2 core and two perchlorate ions as counter anions, in which the nickel(II) ion assumes an octahedral coordination geometry with N3O3 donor atoms consisting of four donor atoms of a quadridentate ligand, a bridging phenoxo-oxygen atom, and an oxygen atom of methanol. A ferromagnetic interaction with J = +7.1 cm-1 operates between the two high-spin nickel(II) ions. 1 undergoes a deprotonation of the imidazole proton under basic conditions to give the deprotonated complex 1′. The crystal of 1′ consists of an electrically-neutral imidazolate-bridged cyclic-tetranuclear molecule with Ni-Ni = 6.339(2) Å and Ni-N = 2.051(7) Å, in which the nickel(II) ion assumes a square-pyramidal geometry with N4O donor atoms consisting of the quadridentate ligand and an imidazolate nitrogen of the adjacent nickel (II) complex. An antiferromagnetic interaction with J= -6.3 cm-l is observed between the adjacent nickel(II) ions through the imidazolate group. Since the corresponding deprotonated copper(II) complex with the same ligand assumed an imidazolate-bridged zigzag-chain structure, the result with the nickel(II) complex demonstrates a very marked influence of the metal ion on the formation of the assembly structure.
No preview · Article · Aug 1998 · Bulletin of the Chemical Society of Japan
[Show abstract][Hide abstract] ABSTRACT: Synthesis and X-ray crystal structure of the deprotonated complex with a tripod hexadentate ligand involving three imidazole groups were reported. The deprotonated complex assumed a chiral two-dimensional quasi-honey-comb structure made by the network of hydrogen bonds.
No preview · Article · Jul 1998 · Chemistry Letters
[Show abstract][Hide abstract] ABSTRACT: Dipotassium N,N′-1,2-phenylenebis(2-carbamoyl-κN-phenolato-κO]cuprate(II)), K2[CuL], reacts with nickel(II), cobalt(II), and zinc(II) acetates, and 2,2′-bipyridine in a 1 : 1 : 2 molar ratio in methanol to yield the hetero-metal dinuclear complexes [CuLNi(bpy)2]·3MeOH (1·3MeOH), [CuLCo(bpy)2]·2DMF (2·2DMF), and [CuLZn(bpy)2]·1.5H2O (3), respectively. Crystal data for 1 : P1 (No. 2) with a = 15.969(2), b = 23.494(3), c = 12.705(2) Å, α = 92.15(1), β = 91.652(10), γ = 101.521(9)°, V = 4663(1) Å3, and Z = 4; 2, P21/c (No. 14) with a = 12.604(3), b = 24.364(5), c = 13.823(2) Å, β = 94.49(1)°, V = 4231(1) Å3, and Z = 4. 1 and 2 have a similar discrete di-μ-phenoxo-bridged dinuclear structure, in which the Cu(II) ion assumes a square-planar geometry with the N2O2 donors atoms consisting of two amido nitrogen and two phenoxo oxygen atoms of the tetradentate ligand, and the Ni(II) or Co(II) ion assumes an octahedral geometry with the two phenoxo oxygens of the tetradentate ligand and four nitrogen atoms from two bpy. The magnetic-susceptibility data were reproduced based on the isotropic spin Hamiltonian H = −2JS1·S2 with J = −118.0 cm−1, (S1, S2) = (1/2, 1) for 1 and J = −11.0 cm−1, (S1, S2) = (1/2, 3/2) for 2, respectively. When 3 was recrystallized from DMF/2-propanol, [CuLZn(bpy)]2·2DMF (3′) was obtained. The 1 : 1 : 1 reaction of K2[CuL′], copper(II) acetate monohydrate, and 2,2′-bipyridine in methanol yielded [CuL′Cu(bpy)]2·2MeOH (4), (H4L′ = 1,2-bis(hydroxybenzamido)ethane). Crystal data for 3′: Pbca (No. 61) with a = 19.143(2), b = 18.195(2), c = 16.832(3) Å, and Z = 4; 4, P21/n (No. 14) with a = 13.407(1), b = 13.172(4), c = 13.764(2) Å, β = 94.11(1)°, V = 2424.4(8) Å3, and Z = 4. 3′ and 4 have a similar cyclic di-μ-phenoxo-μ-amido-bridged tetranuclear structure, which can be described as two di-μ-phenoxo-bridged dinuclear units bridged together by the coordination of one amido oxygen atom from each dinuclear unit to the zinc(II) or copper(II) ion of the other dinuclear unit, with Zn(1)–O(3)* = 2.004(3) and Cu(2)–O(4)* = 1.924(4) Å bond distances, respectively. In the tetranuclear structure, the copper(II) ion coordinated by the tetradentate ligand assumes a square-planar geometry and the zinc(II) or the other copper(II) ion assumes a square-pyramidal coordination geometry with two phenoxo-oxygen atoms, two nitrogen atoms of bpy, and one amido oxygen atom. The magnetic susceptibility of 4 was reproduced by an equation derived from the H = −2J(S1·S2 + S3·S4) − 2J′(S2·S3 + S4·S1) spin Hamiltonian with J = −14.6 cm−1 and J′ = −4.0 cm−1.
No preview · Article · Jan 1998 · Bulletin of the Chemical Society of Japan