A simple change of the substituents in the bridging ligand allows tuning of the ordering temperatures, Tc, in the new family of layered chiral magnets A[M(II)M(III)(X2An)3]·G (A = [(H3O)(phz)3](+) (phz = phenazine) or NBu4(+); X2An(2-) = C6O4X2(2-) = 2,5-dihydroxy-1,4-benzoquinone derivative dianion, with M(III) = Cr, Fe; M(II) = Mn, Fe, Co, etc.; X = Cl, Br, I, H; G = water or acetone). Depending on the nature of X, an increase in Tc from ca. 5.5 to 6.3, 8.2, and 11.0 K (for X = Cl, Br, I, and H, respectively) is observed in the MnCr derivative. Furthermore, the presence of the chiral cation [(H3O)(phz)3](+), formed by the association of a hydronium ion with three phenazine molecules, leads to a chiral structure where the Δ-[(H3O)(phz)3](+) cations are always located below the Δ-[Cr(Cl2An)3](3-) centers, leading to a very unusual localization of both kinds of metals (Cr and Mn) and to an eclipsed disposition of the layers. This eclipsed disposition generates hexagonal channels with a void volume of ca. 20% where guest molecules (acetone and water) can be reversibly absorbed. Here we present the structural and magnetic characterization of this new family of anilato-based molecular magnets.
Starting from 1,3-dimethyl-4-imidazoline-2-selone (1), 1,2-bis(2-selenoxo-3-methyl-4-imidazolinyl-2-)ethane (3) and 1,3-dimethylimidazolidine-2-selone (4), the following six compounds, [(C(5)H(8)N(2)Se-)(2)](2+).2Br(-) (I), [(C(5)H(8)N(2)Se-)(2)](2+).2I(-) (II), [(C(5)H(8)N(2)Se-)(2)](2+).Cl(-).I(3)(-) (III) [(C(5)H(10)N(2)Se-)(2)](2+).Br(-).IBr(2)(-) (IV), [(C(5)H(7)N(2)Se-)(2)](2+).I(3)(-).(1)/(2)I(4)(-) (V) and [(C(5)H(7)N(2)Se-)(2)](2+).2I(-).CH(3)CN (VI), in which the selenium compounds are oxidized to dications bearing the uncommon -Se-Se- bridge, have been prepared, and I-V crystallographically characterized. I and III were obtained by reacting 1 with IBr and ICl respectively, while II was obtained by reduction of previously described hypervalent selenium compound of 1 (5) bearing the I-Se-I group with elemental tellurium. These three compounds contain the same [(C(5)H(8)N(2)Se-)(2)](2+) dication balanced by two bromides in I, two iodides in II, and Cl(-) and I(3)(-) in III. However, on the basis of the Se-Cl bond length of 2.778(5) Å, III can also be considered as formed by the [(C(5)H(8)N(2)Se-)(2)Cl](+) cation, with I(3)(-) as counterion. Similarly to III, compound IV, which was obtained by reacting 4 with IBr, can be considered as formed by [(C(5)H(10)N(2)Se-)(2)Br](+) cations and IBr(2)(-) anions. As in II, compound V has been prepared by reduction of the hypervalent selenium compound of 3 (6) bearing two I-Se-I groups with elemental tellurium. In V, the [(C(5)H(7)N(2)Se-)(2)](2+) cation is balanced by I(3)(-) and half I(4)(2-) anions. The structural data show that all the cations are very similar, with Se-Se bond lengths ranging from 2.409(2) to 2.440(2) Å. FT-IR and FT-Raman spectra of I-VI allow one to identify two bands around 230 +/- 10 and 193 +/- 5 cm(-1) that are common to all compounds. These bands are generally strong in the FT-Raman and weak in the FT-IR spectra and should contain a contribution of the nu(Se-Se) stretching vibration. The spectra are also in good agreement with the structural features of the polyhalide anions present in the crystals. Crystallographic data are as follows: I is monoclinic, space group P2(1), with a = 9.849(6) Å, b = 11.298(5) Å, c = 7.862(6) Å, beta = 106.44(2) degrees, Z = 2, and R = 0.0362; II is monoclinic, space group P2(1), with a = 8.063(6) Å, b = 11.535(5) Å, c = 10.280(5) Å, beta = 107.13(2) degrees, Z = 2, and R = 0.0429, III is monoclinic, space group P2(1)/n, with a = 10.431(7) Å, b = 18.073(5) Å, c = 11.223(6) Å, beta = 100.76(2) degrees, Z = 4, and R = 0.0490; IV is monoclinic, space group P2(1)/n, with a = 10.298(5) Å, b = 18.428(7) Å, c = 11.475(6) Å, beta = 104.10(4) degrees, Z = 4, and R = 0.0300; V is triclinic, space group P&onemacr;, with a = 7.456(6) Å, b = 11.988(5) Å, c = 12.508(5) Å, alpha = 79.32(2) degrees, beta = 85.49(2) degrees, gamma = 80.62(2) degrees, Z = 2, and R = 0.0340.
FT-Raman spectra of some polyiodides and of a series of D · I2 charge-transfer complexes (where D is a molecule containing the thione or selone groups as donors), all characterized by x-ray diffraction, are reported. For the adducts with the thione compounds, which can be considered weak or medium-weak complexes, an empirical linear correlation between the frequency of the v(I-I) stretching vibrations and the d(I-I) bond distances has been found. Some polyiodides show FT-Raman spectra that are indistinguishable with respect to those displayed by the neutral complexes of weak or medium-weak strength; in such cases, the polyiodide can be regarded as a diiodine molecule, perturbed by an I n ( n = 1,3,…) donor. Polyiodides of this type show Raman absorptions falling in the linear correlation.
A simple method to obtain in high yields mixed-ligand nickel-dithiolene complexes, which show strong negative solvatochromism and negative first molecular hyperpolarizability, and the use of Raman spectroscopy to establish the extent of electronic delocalisation in these complexes, are reported.
Synthesis, characterization, NLO properties, and theoretical studies of the mixed-ligand dithiolene complexes of the nickel triad [M(II)(Bz(2)pipdt)(mnt)] (Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione, mnt = maleonitriledithiolato, M(II) = Ni, 1, Pd, 2, Pt, 3) are reported. Molecular structural characterization of 1-3 points out that four sulfur atoms are in a slightly distorted square-planar geometry. While the M-S bond distances are only slightly different, comparison of the C-C and C-S bonds in the C(2)S(2)MS(2)C(2) core allows us to point out a significant difference between the C-C and the C-S distances in Bz(2)pipdt and mnt. These findings suggest assigning a dithiolato character to mnt (pull ligand) and a dithione one (push ligand) to Bz(2)pipdt. Cyclic voltammetry of 1-3 exhibits two reversible reduction waves and a broad irreversible oxidation wave. These complexes are characterized in the visible region by a peak of moderately strong intensity, which undergoes negative solvatochromism. The molecular quadratic optical nonlinearities were determined by the EFISH technique, which provided the following values μβ(λ) (10(-48) esu) = -1436 (1), -1450 (2), and -1950 (3) converted in μβ(0) (10(-48) esu) = -463 (1), -684 (2), and -822 (3), showing that these complexes exhibit large negative second-order polarizabilities whose values depend on the metal, being highest for the Pt compound. DFT and TD-DFT calculations on 1-3 allow us to correlate geometries and electronic structures. Moreover, the first molecular hyperpolarizabilities have been calculated, and the results obtained support that the most appealing candidate as a second-order NLO chromophore is the platinum compound. This is due to (i) the most extensive mixture of the dithione/metal/dithiolato orbitals, (ii) the influence of the electric field of the solvent on the frontier orbitals that maximizes the difference in dipole moments between the excited and the ground state, and (iii) the largest oscillator strength in the platinum case vs nickel and palladium ones.
In resonance Raman (RR) spectroscopy, the laser excitation sources have often been found to be destructive towards polyiodides if compared with the milder conditions under which the Fourier transform Raman (FT-R) technique operates. In fact, our FT-R spectra of some model polyiodides—[(CH3)4N]I5 (I5− bent), [(C2H5)4N]I7, and [(CH3)4N]I9—are significantly different from the literature RR data, give evidence of decomposition of the samples in RR, and are in agreement, respectively, with the I− · 2I2, I3− · 2I2 and (I− · 2I2) · 2I2 descriptions. In addition to the above-cited cases, the FT-R spectra of (Mn(modtc)3]Is (modtc = morpholine carbodithioato) and (moH]I5 (moH = morpholinium) are reported. The crystal structures indicate that in these two compounds the I5 anions can be properly described as I− · 2I2 and I3− · I2, respectively, and FT-R spectra agree well with this formulation. Moreover, the first FT-R spectrum of an I164– anion in [mo2ttl]2I16, ([mo2ttl]2+ = 3,5-di( N-morpholinio)-1,2,4-trithiolane), whose X-ray structure shows a sequence of two I3− … I2 … I− ·I2 (I82–) interacting anions, is reported. A close correlation of the FT-Raman peaks with the molecular species, identified by the interatomic distances, is also observed in this case. Thus, a combination of X-ray structural data and FT-R data can provide a reasonable interpretation of the nature of the acceptor iodine moiety in charge-transfer polyiodide complexes.
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