The synthesis, structure and CO-releasing properties of a number of new tricarbonyl rhenium(i) complexes with 5-substituted-6-amino-1,3-dimethyluracils are reported and their structural features discussed on the basis of both spectral and X-ray crystallographic analyses. The 5-substituent library includes -N[double bond, length as m-dash]CH-2py (DAAUPic) and -CH[double bond, length as m-dash]N-N[double bond, length as m-dash]CH-2py (FDUHzPic) as additional metal binding components and chloride, acetonitrile or pyridine acting as ancillary ligands. The compounds have been identified by elemental analysis, NMR, MS and IR spectroscopy. In addition, [ReCl(CO)(DAAUPic)], [Re(CO)(FDUHzPic)py]ClO, [Re(CO)(FDUHzPic)py]PF, [ReCl(CO)(FDUHzPic)] and [ReCl(CO)(FDUHzPicH)(HO)] structures have been solved by X-ray diffraction methods. These studies have clearly shown that the preferred coordination mode to rhenium takes place through the (N1F,N52)-pyridin-2-yl-methyleneamine moiety, the uracil coordinative availability (O4-N51 or N6-N51) being used only to bind the second metal center. The CO-releasing ability of these rhenium compounds has been investigated by the reaction with myoglobin; the corresponding studies have revealed that two of the mononuclear complexes and their related binuclear analogues are able to release CO to a moderate extent. This ability has also been theoretically assessed through a QTAIM analysis. The results, although non-conclusive, may explain somehow possible different preferences in CO releasing power after a comparison between the nature of Re-CO links in mononuclear and binuclear compounds.
The synthesis and characterization of the first thiosemicarbazone-lumazine (TSCLMH=the thiosemicarbazone of 6-acetyl-1,3,7-trimethyllumazine) hybrid ligand is reported. The influence of the conformation of this compound on its energy and the atomic contribution to the molecular orbitals have been theoretically investigated. Ni(II), Cu(I), Zn(II), and Cd(II) complexes of this ligand have been synthesized and characterized by elemental analysis, thermogravimetric studies, IR, 1H, 13C, and 15N NMR, and UV-vis-NIR spectroscopy, magnetic measurements, and X-ray crystallography. Four types of coordination modes for the ligand may be predicted: (a) double bidentate; (b) tetradentate; (c) tridentate; (d) bidentate. Structures of representative complexes of types a, b, and d have been determined by X-ray crystallography. In the [Cu(TSCLMH)]2(ClO4)2 complex, TSCLMH acts as a doubly bidentate bridging ligand forming a dimer with a Cu...Cu distance of 2.876 A. The geometry around the metal ion is trigonally distorted tetrahedral with a relatively long (four-atom) bridge between the metal centers instead of the shorter, mainly single atom, bridges present in other thiosemicarbazone derivatives complexes. In the [Cd(NO3)2(TSCLMH)(EtOH)] complex, the metal ion displays eight-coordinated geometry with the TSCLMH ligand acting in a tetradentate planar fashion and two nitrate anions, one monodentate and the other bidentate. The coordination polyhedron in [Cd(TSCLM)2(H2O)].MeOH.2H2O is a square pyramid with two monoanionic ligands acting as bidentate NS donors and a water molecule completing the coordination sphere. Fluorescence spectroscopic properties of TSCLMH have been studied as well as the changes in position and intensity of fluorescence bands caused by the complexation with different metal ions (Ni2+, Cu+, Zn2+, Cd2+).
The development of
fluorescence materials with
switched
on
/
off
emission has attracted great attention
owing to the potential application of these materials in chemical
sensing. In this work, the photophysical properties of a series of
original 2-(2′-hydroxyphenyl)pyrimidines were thoroughly studied.
The compounds were prepared by following well-established and straightforward
methodologies and showed very little or null photoluminescence both
in solution and in the solid state. This absence of emission can be
explained by a fast proton transfer from the OH group to the nitrogen
atoms of the pyrimidine ring to yield an excited tautomer that deactivates
through a nonradiative pathway. The key role of the OH group in the
emission quenching was demonstrated by the preparation of 2′-unsubstituted
derivatives, all of which exhibited violet or blue luminescence. Single
crystals of some compounds suitable for an X-ray diffraction analysis
could be obtained, which permitted us to investigate inter- and intramolecular
interactions and molecular packing structures. The protonation of
the pyrimidine ring by an addition of trifluoroacetic acid inhibited
the excited-state intramolecular proton transfer (ESIPT) process,
causing a reversible
switch on
fluorescence response
detectable by the naked eye. This acidochromic behavior allows 2-(2′-hydroxyphenyl)pyrimidines
to be used as solid-state acid–base vapor sensors and anticounterfeiting
agents. Extensive density functional theory and its time-dependent
counterpart calculations at the M06-2
X
/6-31+G** level
of theory were performed to rationalize all the experimental results
and understand the impact of protonation on the different optical
transitions.
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