RT Journal Article
T1 Dimeric tetrabromo-p-quinodimethanes: synthesis and structural/electronic properties
A1 Vicent, Diego
A1 Pérez-Escribano, Manuel
A1 Cárdenas-Valdivia, Abel
A1 Barragán, Ana
A1 Calbo, Joaquín
A1 Urgel, José
A1 Écija, David
A1 Santos Barahona, José Manuel
A1 Casado, Juan
A1 Ortí, Enrique
A1 Martín León, Nazario
AB Despite their great potential as molecular building blocks for organic synthesis, tetrabromo-p-quinodimethanes (TBQs) are a relatively unknown family of compounds. Herein, we showcase a series of five derivatives incorporating two tetrabromo-anthraquinodimethane (TBAQ) units linked by π-conjugated spacers of different nature and length. The resulting dimers TBQ1–5 are fully characterised by means of thorough spectroscopic measurements and theoretical calculations. Interestingly, owing to the steric hindrance imposed by the four bulky bromine atoms, the TBAQ fragments adopt a characteristically warped geometry, somehow resemblant of a butterfly, and the novel dimers show a complex NMR pattern with signal splittings. To ascertain whether dynamic processes regarding fluxional inversion of the butterfly configurations are involved, first-principles calculations assessing the interconversion energy barriers are performed. Three possible stereoisomers are predicted involving two diastereomers, thus accounting for the observed NMR spectra. The rotational freedom of the TBAQ units around the π-conjugated linker influences the structural and electronic properties of TBQ1–5 and modulates the electronic communication between the terminal TBAQ moieties. The role of the linker on the electronic properties is investigated by Raman and UV-vis spectroscopies, theoretical calculations and UV-vis measurements at low temperature. TBQ1–5 are of interest as less-explored structural building precursors for a variety of scientific areas. Finally, the sublimation, self-assembly and reactivity on Au(111) of TBQ3 is assessed.
PB Royal Society of Chemistry
SN 2041-6520
YR 2023
FD 2023
LK https://hdl.handle.net/20.500.14352/93472
UL https://hdl.handle.net/20.500.14352/93472
LA eng
NO Vicent, D. J.; Pérez-Escribano, M.; Cárdenas-Valdivia, A.; Barragán, A.; Calbo, J.; Urgel, J. I.; Écija, D.; Santos, J.; Casado, J.; Ortí, E.; Martín, N. Dimeric tetrabromo-p-quinodimethanes: synthesis and structural/electronic properties. Chem. Sci. 2023, 14, 10112-10120 DOI:10.1039/D3SC01615C.
NO Generalitat Valenciana
NO Junta de Andalucía
NO Comunidad de Madrid
NO European Commission
NO Ministerio de Ciencia, Innovación y Universidades (España)
DS Docta Complutense
RD 24 abr 2025