Anion-directed synthesis of metal-organic frameworks based on 2-picolinate Cu(II) complexes: a ferromagnetic alternating chain and two unprecedented ferromagnetic fish backbone chains

Three new polynuclear copper(II) complexes of 2-picolinic acid (Hpic), {[Cu-2(pic)(3)(H2O)]ClO4}(n) (1), {[Cu-2(pic)(3)(H2O)]BF4}(n) (2), and [Cu-2(pic)3(H2O)(2)(NO3)](n) (3), have been synthesized by reaction of the "metalloligand" [Cu-(pic)(2)] with the corresponding copper(II) salts. The compounds are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. Compounds 1 and 2 are isomorphous and crystallize in the triclinic system with space group P (1) over bar, while 3 crystallizes in the monoclinic system with space group P2(1)/n. The structural analyses reveal that complexes 1 and 2 are constructed by "fish backbone" chains through syn-anti (equatorial-equatorial) carboxylate bridges, which are linked to one another by syn-anti (equatorial-axial) carboxylate bridges, giving rise to a rectangular grid-like two-dimensional net. Complex 3 is formed by alternating chains of syn-anti carboxylate-bridged copper(II) atoms, which are linked together by strong H bonds involving coordinated nitrate ions and water molecules and uncoordinated oxygen atoms from carboxylate groups. The different coordination ability of the anions along with their involvement in the H-bonding network seems to be responsible for the difference in the final polymeric structures. Variable-temperature (2-300 K) magnetic susceptibility measurement shows the presence of weak ferromagnetic coupling for all three complexes that have been fitted with a fish backbone model developed for 1 and 2 (J = 1.74 and 0.99 cm(-1); J' = 0.19 and 0.25 cm(-1), respectively) and an alternating chain model for 3 (J = 1.19 cm(-1) and J' = 1.19 cm(-1)).

Synthesis and photoreactivity of aryl substituted 4,5-dithienyl[1,3]dithiol-2-ones

UV irradiation of hitherto unknown 4,5-bis-benzol[b]thiophen-3-yl-[1,3]dithiol-2-one gave 3-(3-benzo[b]thienyl)-thieno[3,4-c]benzo[ e][1,2]dithine by loss of carbon monoxide and rearrangement, whereas 4,5-bis-(2-bromo-phenyl)-[1,3]dithiol-2-one gave a polymeric material containing S-S bridges. The Structures of both photoproducts were demonstrated on the basis of chemical behaviour and/or X-ray diffraction. (C) 2009 Elsevier Ltd. All rights reserved.

Cascade dicopper architectures of a dibenzodioxatetraazamacrocycle

The dibenzodioxatetraazamacrocycle [26]pbz(2)N(4)O(2) was characterised by single crystal X-ray diffraction and the protonation constants of this compound and the stability constants of its copper(II) and lead(II) complexes were determined by potentiometry in water at 298.2 K in 0.10 mol dm(-3) in KNO3. Mono- and dinuclear complexes were found for both metal ions, the dinuclear complexes being the main species in the 5-7.5 pH range for copper(II) and 7.5-8.5 for lead(II). As expected the values of the stability constants for the copper(II) complexes are lower than those for related macrocycles containing only nitrogen atoms. The presence of mono- and dinuclear copper complexes was also confirmed by electrospray ionization mass spectrometry. These results suggest that the symmetric macrocyclic cavity of [26]pbZ(2)N(4)O(2) has enough space for the coordination of two metal ions. Additionally, NMR spectroscopy showed that the dinuclear complex of lead(II) has high symmetry. The equilibrium constants of the dinuclear copper(II) complexes and dicarboxylate anions (oxalate, malonate and succinate) were also determined in 0.10 mol dm-3 aqueous KNO3 solution. Only species containing one anion, Cu(2)H(h)LA((2+h)), were found, strongly suggesting that the anion bridges the two copper(II) ions. The binding constants of the cascade species formed by [Cu-2[26]pbZ(2)N(4)O(2)(H2O)(4+) with dicarboxylate anions decrease with the increase in length of the alkyl chain of the anion, a fact which was attributed to a higher conformational energy necessary for the rearrangement of the macrocycle to accommodate the larger anions bridging the two copper(II) centres. The variation of the magnetic susceptibility with temperature Of [Cu-2(H-2[26]pbz(2)N(4)O(2))(oxa)(3)]-4H(2)O and [Cu-2([26]pbz(2)N(4)O(2))(suc)Cl-2] were measured and the two complexes showed different behaviour. (c) 2007 Elsevier Ltd. All rights reserved.

Facile synthesis of Cu(II) complexes of monocondensed N,N,N donor Schiff base ligands: crystal structure, spectroscopic and magnetic properties

Four new copper(II) complexes, [((CuLN3)-N-1)(2)](ClO4)(2) (1), [(CuL2 N-3)(2)](ClO4)(2) (2), [CuL3(N-3)ClO4)](n) (3) and [CuL4(mu-1,1-N-3)(mu-1,3-N-3)(ClO4)](n) (4) where L-1 = N-1-pyridin-2-yl-methylene-propane-1,3-diamine, L-2 = N-1-(1-pyridin-2-yl-ethylidene)propane-1,3-diamine, L-3 =N-1-(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine and L-4=N-1-(1-pyridin-2-yl-ethylidene)propane-1,2-diamine are four tridentate N,N,N donor Schiff base ligands, have been derived and structurally characterized by X-ray crystallography. Compounds 1 and 2 consist of double basal-apical end-on (EO) azide bridged dinuclear Cu-II complexes with square-pyramidal geometry. In complex 3 the square planar mononuclear [CuL3 (N-3)] units are linked by weakly coordinated perchlorate ions in the axial positions of Cu-II to form a one-dimensional chain. Two such chains are connected by hydrogen bonds involving perchlorate ions and azide groups. Compound 4 consists of 1-D chains in which the Cu-II ions with a square-pyramidal geometry are alternately bridged by single EO and end-to-end (EE) azido ligands, both adopting a basal-apical disposition. Variable temperature (300-2 K) magnetic susceptibility measurements and magnetization measurements at 2 K have been performed. The results reveal that complexes 1 and 2 are antiferromagnetically coupled through azido bridges (J= -12.18 +/- 0.09 and -4.43 +/- 0.1 cm(-1) for 1 and 2, respectively). Complex 3 shows two different magnetic interactions through the two kinds of hydrogen bonds; one is antiferromagnetic (J(1) = - 9.69 +/- 0.03 cm(-1)) and the other is ferromagnetic (J(2) = 1.00 +/- 0.01 cm(-1)). From a magnetic point of view complex 4 is a ferromagnetic dinuclear complex (J= 1.91 +/- 0.01 cm(-1)) coupled through the EO bridge only. The coupling through the EE bridge is practically nil as the N(azido)-Cu-II (axial) distance (2.643 angstrom) is too long. (C) 2006 Elsevier Ltd. All rights reserved.

Bis[1,1 '-N,N '-(2-picolyl)aminomethyl]ferrocene as a redox sensor for transition metal ions

The compound bis[1,1'-N,N'-(2-picolyl) aminomethyl] ferrocene, L-1, was synthesized. The protonation constants of this ligand and the stability constants of its complexes with Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ were determined in aqueous solution by potentiometric methods at 25degreesC and at ionic strength 0.10 mol dm(-3) in KNO3. The compound L-1 forms only 1:1 (M:L) complexes with Pb2+ and Cd2+ while with Ni2+ and Cu2+ species of 2:1 ratio were also found. The complexing behaviour of L-1 is regulated by the constraint imposed by the ferrocene in its backbone, leading to lower values of stability constants for complexes of the divalent first row transition metals when compared with related ligands. However, the differences in stability are smaller for the larger metal ions. The structure of the copper complex with L-1 was determined by single-crystal X-ray diffraction and shows that a species of 2:2 ratio is formed. The two copper centres display distorted octahedral geometries and are linked through the two L1 bridges at a long distance of 8.781(10) Angstrom. The electrochemical behaviour of L-1 was studied in the presence of Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+, showing that upon complexation the ferrocene-ferrocenium half-wave potential shifts anodically in relation to that of the free ligand. The maximum electrochemical shift (DeltaE(1/2)) of 268 mV was found in the presence of Pb2+, followed by Cu2+ (218 mV), Ni2+ (152 mV), Zn2+ (111 mV) and Cd2+ (110 mV). Moreover, L-1 is able to electrochemically and selectively sense Cu2+ in the presence of a large excess of the other transition metal cations studied.

Syntheses, structural analyses, and magneto-structural correlations of three polymeric Fe(II) complexes with azide ligand

Three new metal-organic polymeric complexes, [Fe(N-3)(2)(bPP)(2)] (1), [Fe(N-3)(2)(bpe)] (2), and [Fe(N-3)(2)(phen)] (3) [bpp = (1,3-bis(4-pyridyl)-propane), bpe = (1,2-bis(4-pyridyl)-ethane), phen = 1,10-phenanthroline], have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature magnetic measurements in the range 300-2 K. Complexes 1 and 2 crystallize in the monoclinic system, space group C2/c, with the following cell parameters: a = 19.355(4) Angstrom, b = 7.076(2) Angstrom, c = 22.549(4) Angstrom, beta = 119.50(3)degrees, Z = 4, and a = 10.007(14) Angstrom, b = 13.789(18) Angstrom, c = 10.377(14) Angstrom, beta = 103.50(1)degrees, Z = 4, respectively. Complex 3 crystallizes in the triclinic system, space group P (1) over bar, with a = 7.155(12) Angstrom, b = 10.066(14) Angstrom, c = 10.508(14) Angstrom, alpha = 109.57(1)degrees, beta = 104.57(1)degrees, gamma = 105.10(1)degrees, and Z = 2. All coordination polymers exhibit octahedral Fe(II) nodes. The structural determination of 1 reveals a parallel interpenetrated structure of 2D layers of (4,4) topology, formed by Fe(II) nodes linked through bpp ligands, while mono-coordinated azide anions are pendant from the corrugated sheet. Complex 2 has a 2D arrangement constructed through 1D double end-to-end azide bridged iron(11) chains interconnected through bpe ligands. Complex 3 shows a polymeric arrangement where the metal ions are interlinked through pairs of end-on and end-to-end azide ligands exhibiting a zigzag arrangement of metals (Fe-Fe-Fe angle of 111.18degrees) and an intermetallic separation of 3.347 Angstrom (through the EO azide) and of 5.229 Angstrom (EE azide). Variable-temperature magnetic susceptibility data suggest that there is no magnetic interaction between the metal centers in 1, whereas in 2 there is an antiferromagnetic interaction through the end-to-end azide bridge. Complex 3 shows ferro- as well as anti-ferromagnetic interactions between the metal centers generated through the alternating end-on and end-to-end azide bridges. Complex I has been modeled using the D parameter (considering distorted octahedral Fe(II) geometry and with any possible J value equal to zero) and complex 2 has been modeled as a one-dimensional system with classical and/or quantum spin where we have used two possible full diagonalization processes: without and with the D parameter, considering the important distortions of the Fe(II) ions. For complex 3, the alternating coupling model impedes a mathematical solution for the modeling as classical spins. With quantum spin, the modeling has been made as in 2.

A novel trinuclear nickel(II) complex of an unsymmetrical tetradentate ligand involving bridging oxime and acetylacetone functions

A novel trinuclear nickel(II) complex, [Ni-3(L)(2)(H2O)(2)](ClO4)(2), where L is a bridging unsymmetrical tetradentate ligand, involving o-phenylenediamine, diacetyl monoxime and acetylacetone (H2L = 4-[2-(3-hydroxy-1-methyl-but-2-enylideneamino)-phenylimino]-pentan-2- one oxime) has been synthesized and characterized structurally. In the complex, an octahedral Ni( II) centre is held in the middle by two square planar units with the aid of oxime and ketonic bridges. (c) 2007 Elsevier B. V. All rights reserved.

Influence of counter anions on the structures and magnetic properties of trinuclear Cu(II) complexes containing a mu(3)-OH core and Schiff base ligands

Four trinuclear Cu(II) complexes, [(CuL1)(3)(mu(3)-OH)](NO3)(2) (1), [(CuL2)(3)(mu(3)-OH)](I)(2)center dot H2O (2), [(CuL3)(3)(mu(3)-OH)](I)(2) (3) and [(CuL1)(3)(mu(3)-OH)][(CuI3)-I-1] (4), where HL1 (8-amino-4-methyl-5-azaoct-3-en-2-one), HL2 [7-amino-4-methyl-5-azaoct-3-en-2-one] and HL3 [7-amino-4-methyl-5-azahept-3-en-2- one] are the three tridentate Schiff bases, have been synthesized and structurally characterized by X-ray crystallography. All four complexes contain a partial cubane core, [(CuL)(3)(mu(3)-OH)](2+) in which the three [CuL] subunits are interconnected through two types of oxygen bridges afforded by the oxygen atoms of the ligands and the central OH- group. The copper(II) ions are in a distorted square-pyramidal environment. The equatorial plane consists of the bridging oxygen of the central OH- group together with three atoms (N, N, O) from the Schiff base. The oxygen atom of the Schiff base also coordinates to the axial position of Cu(II) of another subunit to form the cyclic trimer. Magnetic susceptibilities have been determined for these complexes over the temperature range of 2-300 K. The isotropic Hamiltonian, H = -J(12)S(1)S(2) - J(13)S(1)S(3) - J(23)S(2)S(3) has been used to interpret the magnetic data. The best fit parameters obtained are: J = - 54.98 cm(-1) g = 2.24 for 1; J = - 56.66 cm(-1), g = 2.19 for 2; J = -44.39 cm(-1), g = 2.16 for 3; J = - 89.92 cm(-1), g = 2.25 for 4. The EPR data at low temperature indicate that the phenomenon of spin frustration occurs for complexes 1-3. (c) 2007 Elsevier B.V. All rights reserved.

Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine and o-hydroxyacetophenone in Ni-II and Cu-II complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]center dot 2H(2)O (1) of mono-condensed tridentate Schiff base ligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the Nil, as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)(2)center dot 4H(2)O furnishing the complex [NiL(NCS)] (2) and with CuCl2 center dot 2H(2)O in the presence of NaN3 or NH4SCN producing [CuL(N-3)](2) (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)(2)center dot 6H(2)O and Cu(NO3)(2)center dot 3H(2)O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)(2)center dot 6H(2)O or Ni(NO3)(2)center dot 6H(2)O to yield [Ni(hap)(2)] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, Ni-II possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around Cu-II in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around Cu-II is square pyramidal. In both 5 and 6, the Cu-II atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

(Ni-2), (Ni-3), and (Ni-2 + Ni-3): A Unique Example of Isolated and Cocrystallized Ni-2 and Ni-3 Complexes

Structural and magnetic characterization of compound {[Ni-2(L)(2)(OAC)(2)][Ni-3(L)(2) (OAc)(4)]) center dot 2CH(3)CN (3) (HL = the tridentate Schiff base ligand, 2-[(3-methylaminb-propylimino)-methyl]-phenol) shows that it is a rare example of a crystal incorporating a dinuclear Ni(II) compound, [Ni-2(L)(2)(OAc)(2)], and a trinuclear one, [Ni-3(L)(2)(OAC)(4)]. Even more unusual is the fact that both Ni (II) complexes, [Ni-2(L)(2)(OAc)(2)] (1) and [Ni-3(L)(2)(OAc)(4)(H2O)(2)] center dot CH2Cl2 center dot 2CH(3)OH (2), have also been isolated and structurally and magnetically characterized. The structural analysis reveals that the dimeric complexes [Ni-2(L)(2)(OAc)(2)] in cocrystal 3 and in compound 1 are almost identical-in both complexes, the Ni(II) ions possess a distorted octahedral geometry formed by the chelating tridentate ligand (L), a chelating acetate ion, and a bridging phenoxo group with very similar bond angles and distances. On the other hand, compound 2 and the trinuclear complex in the cocrystal 3 show a similar linear centrosymmetric structure with the tridentate ligand coordinated to the terminal Ni(II) and linked to the central Ni(II) by phenoxo and carboxylate bridges. The only difference is that a water molecule found in 2 is not present in the trinuclear unit of complex 3; instead, the coordination sphere is completed by an additional bridging oxygen atom from an acetate ligand. Variable-temperature (2-300 K) magnetic susceptibility measurements show that the dinuclear unit is antiferromagnetically coupled in both compounds (2J = -36.18 and -29.5 cm(-1) in 1 and 3, respectively), whereas the trinuclear unit shows a very weak ferromagnetic coupling in compound 3 (2J = 0.23 cm(-1)) and a weak antiferromagnetic coupling in 2 (2J = -8.7(2) cm(-1)) due to the minor changes in the coordination sphere.

Anion directed template synthesis of Cu(II) complexes of a N,N,O donor mono-condensed Schiff base ligand: A molecular scaffold forming highly ordered H-bonded rectangular grids

Anion directed, template syntheses of two dinuclear copper(II) complexes of mono-condensed Schiff base ligand Hdipn (4-[(3-aminopentylimino)-methyl]-benzene-1,3-diol) involving 2,4- dihydroxybenzaldehyde and 1,3-diaminopentane were realized in the presence of bridging azide and acetate anions. Both complexes, [Cu-2(dipn)(2)(N-3)(2)] (1) and [Cu-2(dip(n))(2)(OAc)(2)] (2) have been characterized by X-ray crystallography. The two mononuclear units are joined together by basal-apical, double end-on azido bridges in complex 1 and by basal-apical, double mono-atomic acetate oxygen-bridges in 2. Both complexes form rectangular grid-like supramolecular structures via H-bonds connecting the azide or acetate anion and the p-hydroxy group of 2,4- dihydroxybenzaldehyde. Variable-temperature (300-2 K) magnetic susceptibility measurements reveal that complex 1 has antiferromagnetic coupling (J = -2.10 cm (1)) through the azide bridge while 2 has intra-dimer ferromagnetic coupling through the acetate bridge and inter-dimer antiferromagnetic coupling through H-bonds (J = 2.85 cm (1), J' = -1.08 cm (1)). (C) 2009 Elsevier B. V. All rights reserved.