Self-assembled architectures with segregated donor and acceptor units of a dyad based on a monopyrrolo-annulated TTF-PTM radical.
An electron donor-acceptor dyad based on a polychlorotriphenylmethyl (PTM) radical subunit linked to a tetrathiafulvalene (TTF) unit through a π-conjugated N-phenyl-pyrrole-vinylene bridge has been synthesized and characterized. The intramolecular electron transfer process and magnetic properties of the radical dyad have been evaluated by cyclic voltammetry, UV/Vis spectroscopy, vibrational spectroscopy, and ESR spectroscopy in solution and in the solid state. The self-assembling abilities of the radical dyad and of its protonated non-radical analogue have been investigated by X-ray crystallographic analysis, which revealed that the radical dyad produced a supramolecular architecture with segregated donor and acceptor units in which the TTF subunits were arranged in 1D herringbone-type stacks. Analysis of the X-ray data at different temperatures suggests that the two inequivalent molecules that form the asymmetric unit of the crystal of the radical dyad evolve into an opposite degree of electronic delocalization as the temperature decreases.
Department of Molecular Nanoscience and Organic Materials, Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra, 08193 Barcelona (Spain).
Manuel
M
Souto
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, 5230 Odense M (Denmark).
Marta V
MV
Solano
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, 5230 Odense M (Denmark).
Morten
M
Jensen
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, 5230 Odense M (Denmark).
Dan
D
Bendixen
Dipartimento di Chimica, Parma University/INSTM-UdR Parma, 43124 Parma (Italy).
Francesca
F
Delchiaro
Dipartimento di Chimica, Parma University/INSTM-UdR Parma, 43124 Parma (Italy).
Alberto
A
Girlando
Dipartimento di Chimica, Parma University/INSTM-UdR Parma, 43124 Parma (Italy).
Anna
A
Painelli
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, 5230 Odense M (Denmark).
Jan O
JO
Jeppesen
Department of Molecular Nanoscience and Organic Materials, Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra, 08193 Barcelona (Spain).
Concepció
C
Rovira
Department of Molecular Nanoscience and Organic Materials, Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra, 08193 Barcelona (Spain).
Imma
I
Ratera
Department of Molecular Nanoscience and Organic Materials, Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra, 08193 Barcelona (Spain). vecianaj@icmab.es.
Jaume
J
Veciana
D004579:Electron Transport; D006571:Heterocyclic Compounds / Q000737:chemistry*; D015394:Molecular Structure
D006571:Heterocyclic Compounds; C063887:tetrathiafulvalene
charge transfer; donor-acceptor systems; radicals; self-assembly; tetrathiafulvalene