Abstract
SummaryPorphyrin–AuIII complexes were found to act as π-electronic cations, which can combine with various counteranions, including π-electronic anions. Single-crystal X-ray analyses revealed the formation of assemblies with contributions of charge-by-charge and charge-segregated assemblies, depending on the geometry and electronic state of the counteranions. Porphyrin–AuIII complexes possessing aliphatic alkyl chains formed dimension-controlled ion-pairing assemblies as thermotropic liquid crystals, whose ionic components were highly organized by π–π stacking and electrostatic interactions.
Highlights
An ordered arrangement of p-electronic species is crucial for the fabrication of functional organic materials such as organic electronic devices including field-effect transistors, light-emitting diodes, and photovoltaic cells (Wurthner, 2005; Nakanishi, 2011; Koch, 2015)
The characterization of the ion pairs, especially the determination of the 1:1 molar ratio of cationic Au0+ and corresponding anions, was conducted via elemental analysis. 19F nuclear magnetic resonance (NMR) was measured to determine molar ratios for the ion pairs with BF4– and PF6
The ion pairs with a p-electronic anion clearly afforded charge-by-charge-based mesophases, which existed at exceptionally wide temperature ranges, in contrast to the assemblies with relatively small anions
Summary
An ordered arrangement of p-electronic species is crucial for the fabrication of functional organic materials such as organic electronic devices including field-effect transistors, light-emitting diodes, and photovoltaic cells (Wurthner, 2005; Nakanishi, 2011; Koch, 2015). An important strategy is the use of AuIII (d8), which provides planar porphyrin–AuIII complexes as stable p-electronic cations that require no axial ligands (Fleischer and Laszlo, 1969; Timkovich and Tulinsky, 1977; Shachter et al, 1987; Brun et al, 1991; Kilsaet al., 2001; Andersson et al, 2002; Che et al, 2003; Eng et al, 2005; Wang et al, 2007; Fortage et al, 2008; Sun et al, 2010; Ou et al, 2011, 2013; He et al, 2014; Preiß et al, 2016, 2017), resulting in the potential formation of ion pairs with various anions. This article reports the first example of dimension-controlled assemblies based on charge-by-charge and charge-segregated modes mainly as liquid crystals consisting of p-electronic systems, with both cationic and anionic building units
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