0000000000428561
AUTHOR
M. Rosario Torres
Concave Tetrathiafulvalene-Type Donors as Supramolecular Partners for Fullerenes
The cap fits! A new class of concave π-extended tetrathiafulvalene (TTF) derivatives, truxene-TTFs, were prepared and characterized, and their self-assembly with fullerenes was investigated (see picture). Truxene-TTFs represent the first example of TTF-related electron donors that serve, without chemical modification, as monotopic receptors for fullerenes in solution. (Chemical Equation Presented). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
Bowl-shape electron donors with absorptions in the visible range of the solar spectrum and their supramolecular assemblies with C 60
We describe the synthesis, electronic, optical and photophysical properties of a family of three electron-donor bowl-shaped organic molecules that absorb light in the whole range of the visible spectrum (up to 800 nm in one case), and associate C60 in solution with binding constants in the range of 104–102 M−1 as measured from both UV-vis and fluorescence titrations in several solvents. These molecules are π-extended derivatives of tetrathiafulvalene, based on a truxene core to which two or three units of dithiole are covalently attached. The inclusion of the bulky dithiole groups is responsible for their bowl-shape geometry, which allows them to associate with C60, and their electron-donor…
Aminopyrimidine-Based Donor–Acceptor Chromophores: Push–Pull versus Aromatic Behaviour
Novel 2-aminopyrimidines substituted with two electron-donor dialkylamino groups and either one dicyanovinyl (4a–d) or one tricyanovinyl (7a–d) electron-acceptor group have been synthesized, and the balance between their push–pull character and their aromatic behaviour has been studied by experimental (spectroscopic, electrochemical and X-ray analysis) and theoretical (DFT/B3LYP/6-31G**) methods. Calculations reveal that the push–pull character is energetically favoured with respect to the preservation of the aromaticity of the pyrimidine ring. X-ray analysis of 7a confirms the theoretical predictions and reveals a strong distortion from planarity due to the steric interaction between the t…
A Straightforward Electroactive π-Extended Tetrathiafulvalene (exTTF) Building Block
The synthesis and X-ray structure of a new and readily available exTTF derivative (6) bearing a methyltriphenylphosphonium bromide moiety as a new building block for the construction of electroactive molecules is reported. The phosphonium salt 6, which was prepared in one step from 2-hydroxymethyl-exTTF as a stable yellow solid in 84 % yield, efficiently undergoes Wittig olefination reactions with a variety of aldehydes to predominantly form the E isomer. Electronic spectra and cyclic voltammetry of the novel compounds reveal the electronic communication between the electroactive units.
MMX Chains and Molecular Species Containing Rh 2 n+ ( n = 4, 5, and 6) Units: Electrical Conductivity in Crystal Phase of MMX Polymers
The control of the experimental conditions in the reaction of Rh 2 (O 2 CCH 3 ) 4 with halides allows the isolation of the novel dirhodium complexes K x [Rh 2 X(O 2 CCH 3 ) 4 ] x ·4xH 2 O (X = Br, 1·4H 2 O and I, 2·4H 2 O) [Rh 2 (O 2 CCH 3 ) 4 Cl] x H 2 O (3·H 2 O), [Rh 2 (O 2 CCH 3 )Cl] x ·4xH 2 O (3·4H 2 O), and {Rh 2 (O 2 CCH 3 ) 4 I 2 ]· 4H 2 0 (4·4H 2 O) containing Rh 2 n+ (n = 4, 5 and 6) units. The X-ray structure determination of compounds 1-4 reveals the presence of dirhodium units in different oxidation states. The polyanionic complexes 1·4H 2 O and 2·4H 2 O containing Rh 2 4+ units give zig-zag chains. In contrast, the partially oxidized complexes 3·H 2 O and 3·4H 2 O containing …
Structure and Properties of One-Dimensional Heterobimetallic Polymers Containing Dicyanoaurate and Dirhodium(II) Fragments
The synthesis and characterization of compound [Rh(2)(O(2)CEt)(4)(H(2)O)(2)] (1) and one-dimensional heterobimetallic polymers K(n){Rh(2)(O(2)CEt)(4)[Au(CN)(2)]}(n) (2) and K(n){Rh(2)(O(2)CMe)(4)[Au(CN)(2)]}(n)·4nH(2)O (3), constructed from dirhodiumtetracarboxylato units, [Rh(2)(O(2)CR)(4)](+), and dicyanoaurate, [Au(CN)(2)](-), fragments are described. In both compounds 2 and 3 the resulting polymeric chains are nonlinear and have in common similar structural parameters, although the solid state supramolecular arrangement is very different. These structural differences explain the fact that complex 2 displays aurophilic interactions while this type of interactions are absent in complex 3.…
Structural, magnetic and electrical properties of one-dimensional tetraamidatodiruthenium compounds
The first bromo and iodo tetraamidatodiruthenium compounds of the type [Ru2X(μ-NHOCC6H4-R)4]n [X = Br, R = o-Me (1), m-Me (2), p-Me (3); X = I, R = o-Me (4), m-Me (5), p-Me (6)] have been prepared using solvothermal or microwave activation procedures. In these reactions ethanol or methanol as solvents have been used to make the synthesis procedures more environment-friendly. Solvothermal synthesis has allowed us to isolate single crystals of these extremely insoluble compounds and the crystal structures of all of them have been determined using single crystal X-ray diffraction. The change of the bridging halide ligand permits us to discuss the properties of these complexes on the basis of t…