Quantitative study of the substituent effects on the electronic absorption and fluorescence spectra of coumarins
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
Authors: Cisse, Lamine; Djande, Abdoulaye; Capo-Chichi, Martine; Khonte, Abdourahmane; Bakhotun, Jean-Pierre; Delattre, Francois; Yoda, Jules; Saba, Adama; Tine, Alphonse; Aaron, Jean-Jacques
Abstract
Because of their important fluorescence properties, coumarins are widely applied in sensing devices. In this paper, the electronic inductive, mesomeric, and electromeric substituent effects on the electronic absorption and fluorescence spectra of 11 substituted coumarins, including NH2, NMe2, NEt2, OH, CF3, CH 3, COOH, Cl, and Br substituents, have been quantitatively studied by means of structure -reactivity relationships. We have applied the Hammett, Brown -Okamoto, and Yukawa -Tsuno correlations to the coumarins electronic absorption and fluorescence spectra wavenumbers and Stokes shifts. The Stokes shift of coumarins decreased when the electron -donor inductive/ mesomeric power of the substituent increased. This Stokes shift decrease was more pronounced when the solvent polarity increased, which might be explained by the electromeric effect increase.
Influence of Dithiolate Bridges on the Structures and Electrocatalytic Performance of Small Bite-Angle PNP-Chelated Diiron Complexes Fe-2(mu-xdt)(CO)(4){kappa(2)-(Ph2P)(2)NR} Related to [FeFe]-Hydrogenases
ORGANOMETALLICS
Authors: Zhao, Pei-Hua; Hu, Meng-Yuan; Li, Jian-Rong; Ma, Zhong-Yi; Wang, Yan-Zhong; He, Jiao; Li, Yu-Long; Liu, Xu-Feng
Abstract
As a further exploration of the asymmetrically substituted diiron models for the active site of [FeFe]-hydrogenases, two new types of small bite-angle amino-diphosphine [(Ph2P)(2)NR; denoted as PNP in this study]-chelated diiron N-phenyl-aza- and ethanedithioate complexes Fe-2(mu-xdt)(CO)(4){kappa(2)-(P(h)2P)(2)NR} (1a-1e) and (2a-2e), respectively, were successfully synthesized by the carbonyl substitution reactions of all-carbonyl diiron complexes Fe-2(mu-xdt)(CO)(6) (xdt = SCH2N(Ph)CH2S (adt(NPh)) and SCH2CH2S (edt)) with PNP (PNP = (Ph2P)(2)NR, R = CMe3, CH2CHMe2, (CH2)(3)Me, (CH2)(3)Si(OEt)(3), and (CH2)(3)NMe2) in the presence of Me3NO center dot 2H(2)O or UV irradiation. All the new complexes obtained above have been well characterized by elemental analysis, FT-IR, NMR spectroscopy, and particularly for 1a, 1b, 2a, and 2d by single-crystal X-ray diffraction analysis. By comparison, P-31{H-1} NMR and X-ray crystallographic studies have clearly revealed that the change of the dithiolate bridge from adt(NPh) to edt has a significant influence on the coordination geometry of the chelating PNP ligands in Fe2S2 complexes, in which the basal-basal configuration in the adt(NPh) complexes 1a-1e is favorable whereas the apical-basal conformation in the edt complexes 2a-2e is main. In addition, the electrochemical properties of complexes 1b and 2b as a pair of representative counterparts are evaluated and compared by cyclic voltammetry in the absence and presence of HOAc as a proton source, indicating that they are found to be electrocatalytically active.