Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(µ3-O)2} Butterfly Core.

The tetranuclear iron(III) compounds [Fe4(µ3-O)2(µ-LZ)4] (1-3) were obtained by reaction of FeCl3 with the shortened salen-type N2O2 tetradentate Schiff bases N,N'-bis(salicylidene)-o-Z-phenylmethanediamine H2LZ (Z = NO2, Cl and OMe, respectively), where the one-carbon bridge between the two iminic nitrogen donor atoms guide preferentially to the formation of oligonuclear species, and the ortho position of the substituent Z on the central phenyl ring selectively drives towards Fe4 bis-oxido clusters. All compounds show a flat almost-symmetric butterfly-like conformation of the {Fe4(µ3-O)2} core, surrounded by the four Schiff base ligands, as depicted by both the X-ray molecular structures of 1 and 2 and the optimized geometries of all derivatives as obtained by UM06/6-311G(d) DFT calculations. The strength of the antiferromagnetic exchange coupling constants between the iron(III) ions varies among the three derivatives, despite their magnetic cores remain structurally almost unvaried, as well as the coordination of the metal ions, with a distorted octahedral environment for the two-body iron ions, Feb, and a pentacoordination with trigonal bipyramidal geometry for the two-wing iron ions, Few. The different magnetic behavior within the series of examined compounds may be ascribed to the influence of the electronic features of Z on the electron density distribution (EDD) of the central {Fe4(µ3-O)2} core, substantiated by a Quantum Theory of Atoms In Molecules (QTAIM) topological analysis of the EDD, as obtained by UM06 calculations 1-3.

Selective Formation, Reactivity, Redox and Magnetic Properties of MnIII and FeIII Dinuclear Complexes with Shortened Salen-Type Schiff Base Ligands.

The reactivity of the shortened salen-type ligands H3salmp, H2salmen and H2sal(p-X)ben with variable para-substituent on the central aromatic ring (X = tBu, Me, H, F, Cl, CF3, NO2) towards the trivalent metal ions manganese(III) and iron(III) is presented. The selective formation of the dinuclear complexes [M2(µ-salmp)2], M = Mn (1a), Fe (2a), [M2(µ-salmen)2(µ-OR)2)], R = Et, Me, H and M = Mn (3a-c) or Fe (4a-c), and (M2(µ-sal[p-X]ben)2(µ-OMe)2), X = tBu, Me, H, F, Cl, CF3, NO2 and M = Mn (5a-g) or Fe (6a-g), could be identified by reaction of the Schiff bases with metal salts and the base NEt3, and their characterization through elemental analysis, infrared spectroscopy, mass spectrometry and single-crystal X-ray diffraction of 2a·2AcOEt, 2a·2CH3CN and 3c·2DMF was performed. In the case of iron(III) and H3salmp, when using NaOH as a base instead of NEt3, the dinuclear complexes [Fe2(µ-salmp)(µ-OR)(salim)2], R = Me, H (2b,c) could be isolated and spectroscopically characterized, including the crystal structure of 2b·1.5H2O, which showed that rupture of one salmp3- to two coordinated salim- ligands and release of one salH molecule occurred. The same hydrolytic tendency could be identified with sal(p-X)ben ligands in the case of iron(III) also by using NEt3 or upon standing in solution, while manganese(III) did not promote such a C-N bond breakage. Cyclic voltammetry studies were performed for 3b, 4b, 5a and 6a, revealing that the iron(III) complexes can be irreversibly reduced to the mixed-valence FeIIFeIII and FeII2 dinuclear species, while the manganese(III) derivatives can be reversibly oxidized to either the mixed-valence MnIIIMnIV or to the MnIV2 dinuclear species. The super-exchange interaction between the metal centers, mediated by the bridging ligands, resulted in being antiferromagnetic (AFM) for the selected dinuclear compounds 3b, 4b, 5a, 5e,5f, 6a and 6e. The coupling constants J (-2JS1·S2 formalism) had values around -13 cm-1 for manganese(III) compounds, among the largest AFM coupling constants reported so far for dinuclear MnIII2 derivatives, while values between -3 and -10 cm-1 were obtained for iron(III) compounds.

Cooperation between cis and trans influences in cis-Pt(II)(PPh(3))(2) complexes: structural, spectroscopic, and computational studies.

The relevance of cis and trans influences of some anionic ligands X and Y in cis-[PtX(2)(PPh(3))(2)] and cis-[PtXY(PPh(3))(2)] complexes have been studied by the X-ray crystal structures of several derivatives (X(2) = (AcO)(2) (3), (NO(3))(2) (5), Br(2) (7), I(2) (11); and XY = Cl(AcO) (2), Cl(NO(3)) (4), and Cl(NO(2)) (13)), density functional theory (DFT) calculations, and one bond Pt-P coupling constants, (1)J(PtP). The latter have allowed an evaluation of the relative magnitude of both influences. It is concluded that such influences act in a cooperative way and that the cis influence is not irrelevant when rationalizing the (1)J(PtP) values, as well as the experimental Pt-P bond distances. On the contrary, in the optimized geometries, evaluated through B3LYP/def2-SVP calculations, the cis influence was not observed, except for compounds ClPh (21), Ph(2) (22), and, to a lesser extent, Cl(NO(2)) (13) and (NO(2))(2) (14). A natural bond order analysis on the optimized structures, however, has shown how the cis influence can be related to the s-character of the Pt hybrid orbital involved in the Pt-P bonds and the net atomic charge on Pt. We have also found that in the X-ray structures of cis-[PtX(2)(PPh(3))(2)] complexes the two Pt-X and the two Pt-P bond lengths are different each other and are related to the conformation of the phosphine groups, rather than to the crystal packing, since this feature is observed also in the optimized geometries.

Push-pull unsymmetrical substitution in nickel(ii) complexes with tetradentate N2O2 Schiff base ligands: synthesis, structures and linear-nonlinear optical studies.

New push-pull (A-D) nickel(ii) compounds of general formula [Ni(5-A-5'-D-saltn)] (3a-3l) with unsymmetrically-substituted N2O2 tetradentate Schiff base ligands are reported here. The ligands 5-A-5'-D-saltn2- (H2saltn = N,N'-bis(salicylidene)diaminopropane) possess differently-substituted salicylaldehyde (A/Dsal) moieties condensed to 1,3-diaminopropane (tn), and carry either an electron acceptor (A = H, Br, or NO2) or donor (D = H, Me, or OMe) group in the para position with respect to the coordinated phenoxido oxygen atoms. These compounds could be obtained by template synthesis involving derivatives [Ni(Gsal)2(H2O)2], 1a-e (G = NO2, Br, H, Me and OMe, respectively) and [Ni(GL)2], 2a-d (GL- = (E)-2-((3-aminopropylimino)methyl)-4-G-phenolate, G = NO2, Br, H and Me, respectively). Scrambling of the ligands and condensation to compounds 3 was suitably achieved by refluxing compounds 1 and 2 that carry the G groups suitable for the desired final A-D combination. Dinuclear intermediates [Ni2(µ-GL)2(G'sal)2] (4a,b,e,f,g) were also detected and isolated. The single-crystal X-ray diffraction structures of [Ni(5'-OMe-saltn)]·CHCl3 (3c·CHCl3), [Ni(5-Br-5'-OMe-saltn)]·EtOH (3g·EtOH) and [Ni(5-NO2-saltn)] (3j) show different degrees of distortion around the central core, leading to saddle-like (3c), planar (3g) and step-like (3j) molecular conformations. DFT geometrical optimization of the compounds showed that, for isolated molecules, the saddle-like conformation is slightly more stable with respect to the other conformations. UV-visible absorption spectra showed structured absorption profiles at about 320-440 nm, whose intensity was amplified by the presence of the nitro group, and this was assigned to a convolution of one metal-to-ligand charge transfer and two intra-ligand charge transfer transitions by TDDFT computations. Surprisingly, UV-visible spectra of the derivatives with Br were comparable to the derivatives with Me, suggesting that in this case the behaviour of the halogen was as a weak electron donor group. The experimental investigation (through electric-field-induced second-harmonic and solvatochromic measurements) of the second-order NLO responses of compounds 3, in conjunction with the theoretical calculations, revealed that the observed NLO efficiency is determined by the combined effect of two almost orthogonal charge transfer directions within the molecules, one along the axis approximately bisecting the donor and the accepting moieties and the other along the A-D axis.

Solid-State Nonlinear Optical Properties of Mononuclear Copper(II) Complexes with Chiral Tridentate and Tetradentate Schiff Base Ligands.

Salen-type metal complexes have been actively studied for their nonlinear optical (NLO) properties, and push-pull compounds with charge asymmetry generated by electron releasing and withdrawing groups have shown promising results. As a continuation of our research in this field and aiming at solid-state features, herein we report on the synthesis of mononuclear copper(II) derivatives bearing either tridentate N2O Schiff bases L(a-c)- and pyridine as the forth ancillary ligand, [Cu(La-c)(py)](ClO4) (1a-c), or unsymmetrically-substituted push-pull tetradentate N2O2 Schiff base ligands, [Cu(5-A-5'-D-saldpen/chxn)] (2a-c), both derived from 5-substituted salicylaldehydes (sal) and the diamines (1R,2R)-1,2-diphenylethanediamine (dpen) and (1S,2S)-1,2-diaminocyclohexane (chxn). All compounds were characterized through elemental analysis, infrared and UV/visible spectroscopies, and mass spectrometry in order to guarantee their purity and assess their charge transfer properties. The structures of 1a-c were determined via single-crystal X-ray diffraction studies. The geometries of cations of 1a-c and of molecules 2a-c were optimized through DFT calculations. The solid-state NLO behavior was measured by the Kurtz-Perry powder technique @1.907 µm. All chiral derivatives possess non-zero quadratic electric susceptibility (χ(2)) and an efficiency of about 0.15-0.45 times that of standard urea.

The role of the atomic charges on the ligands and platinum(II) in affecting the cis and trans influences in [PtXL(PPh3)2]+ complexes (X = NO3, Cl, Br, I; L = 4-substituted pyridines, amines, PPh3). A 31P NMR and DFT investigation.

One bond Pt-P coupling constants (1)J(PtP) of a series of cationic complexes [PtXL(PPh(3))(2)](+) (X = NO(3), Cl, Br, I; L = 4-Z-pyridines, Z = electron withdrawing or releasing groups, 4a-k; or X = Cl, L = NH(3), PhCH(2)NH(2) and (i)PrNH(2), 5a-c) have been used to establish the trans and cis influence sequences of X and pyridines. The crystal structure of compound 4f(BF(4)) with Z = (t)Bu has been resolved. In the pyridine complexes 4a-d (Z = H, variable X), both the trans and cis influence series of the anionic ligands X decrease along the same sequence I > Br > Cl > NO(3), as previously found for [PtX(PPh(3))(3)](+) (X = NO(3), Cl, Br, I, 3a-d), however in 4a-d the cis influence turns out to be more important than the trans. On the contrary, in [PtCl(4-Z-py)(PPh(3))(2)](+) (4b,e-k) the sequence of the trans influence of the 4-Z-pyridines is opposite to that of the cis, the latter being Z = CN > CHO > Br > PhCO > H > Me > (t)Bu > NH(2), i.e. the most basic pyridine gives rise to the lowest cis influence. This correlation was found to hold also for complexes 5a-c (L = amines). All the observed trends have been fully reproduced by B3LYP/def2-SVP DFT calculations, by looking at the relevant optimized bond lengths of selected complexes of type 3, 4 and 5. Subsequent evaluation of the atomic charges, by resorting to two independent methods, i.e., the Natural Bond Order analysis of the wavefunction and the Bader's Quantum Theory of Atoms in Molecules, allowed for rationalization of the origin of the cis and trans influences. The negative charge on the nitrogen atoms of free pyridines becomes more negative upon protonation and even more so when coordinated to the [PtCl(PPh(3))(2)](+) moiety. The least negatively charged nitrogen atom of coordinated pyridines is that of 4-CN-py (the highest cis influencing pyridine derivative), which gives rise to the lowest positive charge on Pt, confirming the relationship between the lowering of the charge on the metal ion and a high cis influence. The trans influence can be described in terms of competition between the charges on the two trans donor atoms. In contrast with the behaviour of pyridines, the positive charge on the phosphorous atom of free PPh(3) increases upon coordination to Pt(II), moreover the PPh(3) ligands acquire a substantial positive charge, thus efficiently delocalising the charge of the cationic complex.

Synthesis, crystal structures and magnetic properties of dinuclear copper(II) compounds with NNO tridentate Schiff base ligands and bridging aliphatic diamine and aromatic diimine linkers.

The synthesis and the characterization of new dinuclear copper(II) compounds of general formula [(L(a-d))(2)Cu(2)(µ-N-N)](ClO(4))(2) (1-6) with either neutral aliphatic diamine (N-N = piperazine, pip) or aromatic diimine (N-N = 4,4'-bipyridine, 4,4'-bipy) linker are reported. The copper ligands L(-) (L(a-) = (E)-2-((2-aminoethylimino)methyl)phenolate, L(b-) = (E)-2-((2-aminopropylimino)methyl)-phenolate, L(c-) = (E)-2-((2-aminoethylimino)methyl)4-nitrophenolate, L(d-) = (E)-2-((2-aminoethylimino)methyl)4-methoxyphenolate) are NNO tridentate Schiff bases derived from the monocondensation of a substituted salicylaldehyde 5-G-salH (G = NO(2), H, OMe) with ethylenediamine, en, or 1,3-propylenediamine, tn. The crystal structures of compounds [(L(a))(2)Cu(2)(MeOH)(2)(µ-4,4'-bipy)](ClO(4))(2) (1·2MeOH), [(L(b))(2)Cu(2)(MeOH)(2)(µ-4,4'-bipy)](ClO(4))(2) (2·2MeOH), [(L(d))(2)Cu(2)(µ-4,4'-bipy)](ClO(4))(2) (4), [(L(a))(2)Cu(2)(µ-pip)](ClO(4))(2) (5) and [(L(b))(2)Cu(2)(µ-pip)](ClO(4))(2) (6) have been determined, revealing the preferred (e-e)-chair conformation of the bridging piperazine in compounds 5 and 6. The presence of hydrogen-bond-mediated intermolecular interactions, that involve the methanol molecules, yields dimers of dinuclear units for 1·2MeOH, and infinite zig-zag chains for 2·2MeOH. The temperature dependences of the magnetic susceptibilities χ(M)(T) for all compounds were measured, indicating the presence of antiferromagnetic Cu-Cu exchange. For the compounds 2-4 with 4,4'-bipy, the coupling constants J are around -1 cm(-1), while in compound 1 no interaction could be detected. The compounds 5 and 6 with piperazine display higher Cu-Cu magnetic interactions through the σ-bonding backbone of the bridging molecule, with J around -8 cm(-1), and the coupling is favoured by the (e-e)-chair conformation of the diamine ring. The non-aromatic, but shorter, linker piperazine gives rise to stronger Cu-Cu antiferromagnetic couplings than the aromatic, but longer, 4,4'-bipyridine. In the latter case, the rotation along the C-C bond between the two pyridyl rings and the consequent non co-planarity of the two copper coordination planes play an important role in determining the magnetic communication. EPR studies reveal that the dinuclear species are not stable in solution, yielding the solvated [(L)Cu(MeOH)](+) and the mononuclear [(L)Cu(N-N)](+) species; it appears that the limited solubility of the dinuclear compounds is responsible for their isolation in the solid state.

Platinum(II) mediated C(sp3)-H activation of tetramethylthiourea.

The C-H activation of the methyl group of tetramethylthiourea by cis-[PtL(2)(NO(3))(2)] (L = phosphine or N-heterocyclic carbene) has been investigated as a function of the ligand L. The presence of an electron-withdrawing group on the tertiary phosphine was found to promote the process. Moreover, when an excess of nitrate anion is present in the reaction mixture, the rate of C-H bond activation is retarded, suggesting the key role of an unsaturated tri-coordinate Pt(II) species as intermediate.

Cis influence in trans-Pt(PPh3)2 complexes.

The cis influence of a series of anionic ligands X and Y has been evaluated through the magnitude of the Pt-P coupling constants for compounds of formula trans-[PtXY(PPh(3))(2)]. The order of decreasing cis influence was found to be I > Cl > SePh approximately SPh approximately SEt > NO(3) > AcO approximately NO(2) > H > Me > Ph > mtc (mtc = N,N-dimethylmonothiocarbamato-S); moreover, the cis influences of the various ligands was found to be additive. The X-ray structures of three representative compounds (t-: X = Cl, Y = NO(3); t-: X = Cl, Y = AcO and t-: X = Y = NO(2)) have also been determined.

Copper(II) complexes of salen analogues with two differently substituted (push-pull) salicylaldehyde moieties. A study on the modulation of electronic asymmetry and nonlinear optical properties.

This paper presents some copper(II) complexes of salen analogues in which the two salicylaldehyde moieties carry different (electron donor, D, and acceptor, A) substituents in position 5, producing a push-pull charge asymmetry. The X-ray structures of some compounds show the presence of pairs of stacked molecules with head-to-tail intermolecular associations. The geometries of all complexes have been optimized through density functional theory (DFT) studies, which have shown that a major influence on the coordination bond lengths is given by the presence of the electron acceptor NO2 group. Such an influence operates mainly on the Cu-phenolato bonds: elongation of the Cu-O distance of the 5-nitrosalicylaldehyde moiety, with a concomitant decrease of the other Cu-O distance; the Cu-N bonds are less affected. The D groups have only a minor influence. The nonlinear optical responses, microgBetavec, of some molecules have been determined by EFISH measurements, and the Beta-vec values have been obtained using the DFT-calculated microg values because solubility problems hampered the experimental measurements of microg of some derivatives; the former, however, have been found to be in agreement with the experimental values that could be obtained. Deconvolution of the absorption bands in the near-UV region has allowed recognition of the charge-transfer (CT) transition, assigned to a ligand-to-metal CT (LMCT) by time-dependent DFT computations; we have then used the solvatochromism of this transition to obtain Beta0 and BetaCT values using the two-state model. These values were compared with those obtained by computational studies, which have also allowed evaluation of the influence of the substituents on the directions of microg and Betatot.