2D-To-3D; Bottom up approach; Crystals structures; Formation mechanism; Lead phthalocyanine; Molecular materials; Molecular networks; Molecular semiconductors; Non-planar molecules; Physisorbed; Chemistry (all); Chemical Engineering (all); Materials Chemistry; General Chemical Engineering; General Chemistry
Abstract :
[en] In this study, a new bottom-up approach is proposed to predict the crystal structure of the substrate-induced polymorph (SIP) of an archetypal molecular semiconductor. In spite of intense efforts, the formation mechanism of SIPs is still not fully understood, and predicting their crystal structure is a very delicate task. Here, we selected lead phthalocyanine (PbPc) as a prototypical molecular material because it is a highly symmetrical yet nonplanar molecule and we demonstrate that the growth and crystal structure of the PbPc SIPs can be templated by the corresponding physisorbed self-assembled molecular networks (SAMNs). Starting from SAMNs of PbPc formed at the solution/graphite interface, the structural and energetic aspects of the assembly were studied by a combination of in situ scanning tunneling microscopy and multiscale computational chemistry approach. Then, the growth of a PbPc SIP on top of the physisorbed monolayer was modeled without prior experimental knowledge, from which the crystal structure of the SIP was predicted. The theoretical prediction of the SIP was verified by determining the crystal structure of PbPc thin films using X-ray diffraction techniques, revealing the formation of a new polymorph of PbPc on the graphite substrate. This study clearly illustrates the correlation between the SAMNs and SIPs, which are traditionally considered as two separate but conceptually connected research areas. This approach is applicable to molecular materials in general to predict the crystal structure of their SIPs.
Disciplines :
Chemistry
Author, co-author :
Hao, Yansong ✱; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux ; Electron Microscopy for Materials Science (EMAT), NANOlab Center of Excellence, University of Antwerp, Antwerp, Belgium
Velpula, Gangamallaiah ; Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Leuven, Belgium
Kaltenegger, Martin; Institute of Solid State Physics, Graz University of Technology, Graz, Austria ; Laboratory of Polymer Chemistry, Faculty of Science, Université Libre de Bruxelles (ULB), Brussels, Belgium
Bodlos, Wolfgang Rao ; Institute of Solid State Physics, Graz University of Technology, Graz, Austria
Vibert, François; Laboratory of Polymer Chemistry, Faculty of Science, Université Libre de Bruxelles (ULB), Brussels, Belgium
Mali, Kunal S. ; Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Leuven, Belgium
De Feyter, Steven ; Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Leuven, Belgium
Resel, Roland ; Institute of Solid State Physics, Graz University of Technology, Graz, Austria
Geerts, Yves Henri ; Laboratory of Polymer Chemistry, Faculty of Science, Université Libre de Bruxelles (ULB), Brussels, Belgium ; International Solvay Institutes of Physics and Chemistry, ULB, Brussels, Belgium
Van Aert, Sandra; Electron Microscopy for Materials Science (EMAT), NANOlab Center of Excellence, University of Antwerp, Antwerp, Belgium
Beljonne, David ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Lazzaroni, Roberto ✱; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
✱ These authors have contributed equally to this work.
Language :
English
Title :
From 2D to 3D: Bridging Self-Assembled Monolayers to a Substrate-Induced Polymorph in a Molecular Semiconductor
R400 - Institut de Recherche en Science et Ingénierie des Matériaux R150 - Institut de Recherche sur les Systèmes Complexes
Funders :
Fonds Wetenschappelijk Onderzoek Gouvernement Wallon Fonds De La Recherche Scientifique - FNRS
Funding text :
This work is supported by FWO and FNRS within the 2Dto3D project of the EOS program (grant number 30489208). The molecular modeling activities in Mons are supported by FNRS (Consortium des Équipements de Calcul Intensif – CÉCI, under Grant 2.5020.11) and by the Walloon Region (ZENOBE Tier-1 supercomputer, under grant 1117545). Y.G. is thankful to the Belgian National Fund for Scientific Research (FNRS) for financial support through research projects BTBT no. 2.4565.11, Phasetrans no. T.0058.14, and Pi-Fast no. T.0072.18. Financial supports from the French Community of Belgium (ARC n° 20061) and by the Walloon Region (WCS no. 1117306 and SOLIDYE no. 1510602) are also acknowledged. D.B. is an FNRS Research Director. G.M.V., K.S.M., and S.D.F. acknowledge support from FWO and KU Leuven-Internal Funds. The authors acknowledge Dr. D. Cornil for his assistance with the STM image simulations and the Synchrotron Elettra Trieste for allocation of synchrotron radiation and thank Luisa Barba for assistance in using beamline XRD1.
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