RT Journal Article
T1 A Trapezoidal Octacyanoquinoid Acceptor Forms Solution and Surface Products by Antiparallel Shape Fitting with Conformational Dipole Momentum Switch
A1 Medina Rivero, Samara
A1 Urieta-Mora, Javier
A1 Molina-Ontoria, Agustín
A1 Martín-Fuentes, Cristina
A1 Urgel, José I.
A1 Zubiria-Ulacia, Maria
A1 Lloveras, Vega
A1 Casanova, David
A1 Martínez, José I.
K1 Aniones
AB A new compound (1) formed by two antiparallelly disposed tetracyano thienoquinoidal units has been synthesized and studied by electrochemistry, UV/Vis-NIR, IR, EPR, and transient spectroscopy. Self-assembly of 1 on a Au(111)surface has been investigated by scanning tunneling microscopy. Experiments have been rationalized by quantum chemicalcalculations. 1 exhibits a unique charge distribution in its anionic form, with a gradient of charge yielding a neatmolecular in-plane electric dipole momentum, which transforms out-of-plane after surface deposition due to twisted!folded conformational change and to partial charge transfer from Au(111). Intermolecular van der Waals interactions andantiparallel trapezoidal shape fitting lead to the formation of an optimal dense on Au(111) two-dimensional assembly of 1.The realization of novel properties emerging upon electronic covalent coupling between chromophores (i.e., bichromophoric systems) is a critical issue for the development of photo- and electrically active systems.[1–3] In this regard, therelative topology and orientation of the p-subchromophores, such as in A + B type p-systems in Figure 1, with 1D linearconjugation, 2D parallel conjugation,[4] 3D orthogonal spiroconjugation[5] or 3D conjugation[6] are key factors. On theother hand, studies of the distribution of the excess of charge in p-conjugated moieties in post-electron transfer events arecentral issues in photophysics and photochemistry, in energy storage[7] and in organic electronics.[8] In addition to thiselectronic provision, its embedment in different molecular forms is of relevance as these can define unique ways of shapefitting in supramolecular and surface assemblies. Joint electronic and molecular shape designs thus allow to buildmolecular-based synthons in a tailored manner towards new bulk and nano organized materials. (...)
PB Wiley
YR 2021
FD 2021-06-04
LK https://hdl.handle.net/10630/24058
UL https://hdl.handle.net/10630/24058
LA eng
NO Medina Rivero, Samara , Urieta-Mora, Javier , Molina-Ontoria, Agustín , Martín-Fuentes, Cristina , Urgel, José I. , Zubiria-Ulacia, Maria , Lloveras, Vega , Casanova, David , Martínez, José I. A Trapezoidal Octacyanoquinoid Acceptor Forms Solution and Surface Products by Antiparallel Shape Fitting with Conformational Dipole Momentum Switch. Angew. Chem. Int. Ed.2021,60, 17887–17892. https://doi.org/10.1002/anie.202104294
NO Funding for open access charge: Universidad de Málaga / CBUA. The authors thank the Spanish Ministry of Science, Innovation and Universities MCIU (projects CTQ2017-83531-R, RED2018-102815-T, MAT2017-85089-C2-1-R), Centro de Excelencia Severo Ochoa grants (SEV-2016-0686, SEV2015-0496 and FUNFUTURE CEX2019-000917-S) and the CAM (QUIMTRONIC-CM project Y2018/NMT-4783). We thank MINECO/FEDER of the Spanish Government (projects PGC2018-098533-B-100 and PID2019-109555GB-I00),the Eusko Jaurlaritza (Basque Government, project PIBA19-0004) and the Junta de Andalucía, Spain (UMA18FEDERJA057). We also thank the Research Central Services (SCAI) of the University of Málaga and the Donostia International Physics Center (DIPC) Computer Center. We thank Dr. Juwon Oh and Prof. Donhgo Kim from the Spectroscopy Laboratory for Functional p-electronic Systems and Department of Chemistry, Yonsei University in Korea for the generous gift of the TRIR and UV/Vis transient absorption spectroscopy data.
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 20 ene 2026