Activation and amplification of the third-order NLO and luminescent responses of a precursor cluster by a supramolecular approach (original) (raw)
Electronic spectra and crystal field analysis of
Chemical Physics Letters, 2007
The 10 K electronic absorption spectrum of Cs 2 NaTmF 6 together with the 355 nm and 455 nm excited luminescence spectra of Cs 2 NaYF 6 :Tm 3+ (1 and 10 at.% Tm 3+ ) have been recorded and assigned in detail. Vibrational structure in the sidebands of the electronic transitions is analogous to that in the spectra of the hexachloroelpasolite systems except that the phonon dispersion is greater. The resulting 4f 12 energy level dataset has been analyzed by a crystal field model including the configuration interaction with the ligand to metal charge transfer configuration. The previously published spectra of Rb 2 NaTmF 6 and Rb 2 NaYF 6 :Tm 3+ have been reinterpreted and shown to be consistent with the present results.
Angew. Chem. Int. Ed.2013, 52, 3222 –3226
Supporting information for this article (including details of experimental and computational studies, and the crystal data for compounds 1 and 2) is available on the WWW under http://dx.doi.
FT-IR and FT-Raman spectra of 4-chlorophenyl quinoline-2-carboxylate were recorded and analyzed. The vibrational wavenumbers were computed using DFT quantum chemical calculations. The data obtained from wavenumber calculations are used to assign vibrational bands obtained experimentally. Potential energy distribution was done using GAR2PED program. The geometrical parameters obtained theoretically are in agreement with the XRD data. NBO analysis, HOMO-LUMO, first hyperpolarizability and molecular electrostatic potential results are also reported. The calculated hyperpolarizability of the title compound is 77.53 times that of the standard NLO material urea and the title compound and its derivatives are attractive object for future studies of nonlinear optical properties. Molecular docking results suggest that the compound might exhibit inhibitory activity against GPb. keywords:DFT; FT-IR; FT-Raman; quinoline; Molecular docking.
6.10a. Inorg. Chem. 31,1233.pdf
The ruthenium complex [Ru2(CloHsN2)(CO),(PiPr3),] (1) (CloHIoN2 = 1,8-diaminonaphthalene) reacts with 1 equiv of HgX, (X = C1, Br, I, 02CCH,, 02CPh, 02CCH2C1, 02CCF3, SCN, ONC) to give the adducts [(1)HgX2], in which the Hg atoms are bonded to both Ru atoms of complex 1. Correlations between the 2J(3'P-199Hg) coupling constants of their 31P NMR spectra and the corresponding halogen electronegativities or acid pK,s have been observed. With the exception of [(1)Hg(O2CCF,),], which does not react with any other mercury(I1) salt, the compounds [(l)HgX,] react with HgX', (X' = C1, Br, I, 02CCH3, 02CPh, 02CCH2C1) to give the insertion products [(l)Hg(p-X'),HgX,] only when X' is more electron-withdrawing than X; otherwise, the addition products [(l)Hg(pX),HgX',] are formed. All reactions of [(l)HgX,] with Hg(02CCF3), give the same substitution product [(l)Hg(02CCF3)2]. The molecular structures of [(l)Hg(O,CCF,),] and [(l)Hg(p-Cl),HgCI,] have been confirmed by X-ray crystallography. [(l)Hg(O,CCF,),]: monoclinic, space group C2/c, a = 23.730 (9) A, b = 12.578 (4) A, c = 14.51 1 (7) A, fl = 94.76 (5)O, Z = 4. [(1)Hg(p-C1),HgC1,]~CH2Cl2: monoclinic, space group P 2 , / n , a = 15.840 (7) A, b = 12.694 (4) A, c = 23.366 (2) A, fl = 105.74 (2)O, Z = 4. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Garda-Granda, S.; Van Der Maelen, J. F. Inorg. Chim. Acta 1991, 185, 187. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Pellinghelli, M. A.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1991, 371. Andreu, P. L.; Cabeza, J. A.; Riera, V.; Robert, F.; Jeannin, Y. J. Organomet. Chem. 1989, 372, C15. Oro, L. A.; Fernindez, M. J.; Modrego, J.; Foces-Foces, C.; Cano, F. H. Angew. Chem., Inr. Ed. Engl. 1984, 23, 913. Fernindez, M. J.; Modrego, J.; Oro, L. A.; Apreda, M. C.; Cano, F. H.; Foces-Foces, C. J. Chem. SOC., Dalton Trans. 1989, 1249. See, for example: Panizo, M.; Cano, M. J. Organomet. Chem. 1984, 266,247. Pardo, M. P.; Cano, M. J. Organomet. Chem. 1983,247,293. Faraone, F.; Lo Schiavo, S.; Bruno, G.; Bombieri, G. J. Chem. Soc., Chem. Commun. 1984, 6. (a) Ermer, S.; King, K.; Rosenberg, E.; Manotti-Lanfredi, A. M.; Tiripicchio, A.; Tiripicchio-Camellini, M. Inorg. Chem. 1983, 22, 1339. (b) Rosenberg, E.; Ryckman, D.; Hsu, I.-N.; Gellert, R. W. Inorg. Chem. 1986, 25, 194. (c) Rosenberg, E.; Hardcastle, K. I.; Day, M. W.; Gobetto, R.; Hajela, S.; Muftikian, R. Organometallics 1991, 10, 203. (d) Fadel, S.; Deutcher, J.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1977, 16, 704. (e) Fajardo, M.; Holden, H. D.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R. J. Chem. SOC., Chem. Commun., 1984, 24. (f) G6mez-Sa1, M. P.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R.; Syed-Mustaffa, S. N. A. B.
Journal of Molecular Structure 1161 (2018) 89e99.pdf
Synthesis, characterization, experimental and theoretical structure of novel Dichloro(bis{2-[1-(4-methoxyphenyl)-1H-1,2,3-triazol-4-yl-kN 3 ]pyridine-kN})metal(II) compounds, metal ¼ Mn, Co and Ni a b s t r a c t The syntheses, characterizations and structures of three novel dichloro(bis{2-[1-(4-methoxyphenyl)-1H-1,2,3-triazol-4-yl-kN 3 ]pyridine-kN})metal(II), [M(L) 2 Cl 2 ], complexes (metal ¼ Mn, Co and Ni) are presented. In the solid state the molecules are arranged in infinite hydrogen-bonded 3D supramolecular structures, further stabilized by weak intermolecular p…p interactions. The DFT results for all the different spin states and isomers of dichloro(bis{2-[1-phenyl-1H-1,2,3-triazol-4-yl-kN 3 ]pyridine-kN}) metal(II) complexes, [M(L 1 ) 2 Cl 2 ], support experimental measurements, namely that (i) d 5 [Mn(L 1 ) 2 Cl 2 ] is high spin with S ¼ 5/2; (ii) d 7 [Co(L 1 ) 2 Cl 2 ] has a spin state of S ¼ 3/2, (iii) d 8 [Ni(L 1 ) 2 Cl 2 ] has a spin state of S ¼ 1; and (iv) for all [M(L 1 ) 2 Cl 2 ] and [M(L) 2 Cl 2 ] complexes, with M ¼ Mn, Co and Ni, the cis-cis-trans and the trans-trans-trans isomers, with the pyridyl groups trans to each other, have the lowest energy.
Physical Chemistry Chemical Physics, 2002
The infrared spectra of dimethyl malonate isolated in low-temperature argon and xenon matrices were studied. Theoretical calculations, carried out at the MP4/6-31G**, MP2/6-31++G** and DFT(B3LYP)/6-311++G** levels, predict two different conformers of nearly equal internal energy, both exhibiting the methyl ester moieties in the cis (C-O) configuration. One of the conformers has C 2 symmetry with the two ester groups crossed symmetrically with respect to the C-C-C plane. This structure is doubly degenerated by symmetry. The other form (gauche) belongs to the C 1 point group. Four identical-by-symmetry minima on the PES correspond to this structure. The energy of this form is predicted (at the MP4 level) to be slightly lower than that of the C 2 conformer. The six minima on the PES can be divided into two groups of three (one C 2 isomer and two C 1 forms in a group). Each structure from one group is related to its counterpart from the other group by the operation of reflection in the C-C-C plane. In each group, the conformers are separated by low energy barriers (less than 2 kJ mol À1 ), while conformational interconversions between the two groups imply a transition state structure with a vis-à -vis orientation of oxygen atoms and thus are associated with considerably higher energy barriers. The infrared spectra of the matrix isolated compound were found to closely match the spectrum predicted for the C 1 conformer. Annealing of the matrices up to 55 K does not lead to significant changes in the spectra, suggesting that the low energy barriers separating the two conformers allow practically all molecules of dimethyl malonate to transform to the more stable gauche conformer, when they are cooled down after landing on the matrix surface. Spectra of the low temperature solid form of the compound (8 K < T < 200 K) also reveal only the presence of the C 1 conformer.