摘要：

IntroductionNowadays it is well known that owing to low charge mobility and exciton diffusion length the performance of most organic semiconductors is significantly poorer than that of commonly used inorganic semiconductors. This may be one of the main obstacles limiting their application as key functional materials in optical and electronic devices. Fortunately, recent studies have demonstrated that constructing highly ordered structures, particularly one-dimensional (1D) columnar nanostructures, of organic and polymeric semiconductors can be an efficient approach to enhance their performance and to extend their application into optoelectronic materials.1,2This is because in 1D columnar nanostructures stacked planar aromatic molecules exhibit π–π interactions which increase the overlap between the electronic wave functions of neighboring molecules,3thereby leading to a high charge-carrier mobility in these nanomaterials along the long axis of the nanostructure.1d,4As important industrial dyes and pigments as well as, in recent years, very promising organic semiconductors, a great number of derivatives of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) have been developed to increase their solubility in common organic solvents and/or to decrease their melting point.5Three major methods have been utilized to modify PTCDA: The first method is a well developed way in which PTCDA reacts with aromatic or aliphatic amines to create perylene tetracarboxylic acid diimides (PTCDIs), the most important derivatives of which structures and properties have been extensively studied.5The second method is to prepare perylene tetracarboxylic tetraesters (PTCTEs)viaesterification of PTCDA.6The final method is to introduce substituents at the carbocyclic scaffold in the so-called bay-area to change the performance of the perylene core.7Most PTCDA derivatives have demonstrated the potential to construct diverse supramolecular structures, mainly because of the strong π–π interaction of the perylene cores.8–14In order to further increase the abundance and diversity of these nanostructures and to further control their functionality, various functional groups were introduced into these compounds in which hydrogen bonding,9electrostatic,10hydrophilic,11amphiphilic,12metal–ligand13and other14interactions play important roles in the self-assembly into nanostructured materials. Nanoscale fibers, wires, tubes, belts/ribbons have been formedviaself-assembly in organic media and lyotropic or thermotropic liquid crystal phases with columnar or smectic arrangements have been observed in their bulk samples. Existing synthesis methods for these PTCDA derivatives require complex and harsh conditions, such as high reaction temperatures, long reaction times, organic solvents (e.g.pyridine, imidazole, quinoline, isoquinolineetc.) and, often, the yield is relatively low. Thus, developing a facile one-pot method to synthesize novel PTCDA derivatives with the ability to form ordered structures should be very welcome to most synthetic chemists in this field.It has been demonstrated that ionic self-assembly (ISA) is a facile and efficient method to build up novel functional materials by complexing two different building blocks with opposite chargesviaelectrostatic interactions.15This technique allows stoichiometric precipitation of starting materials in aqueous solution without other byproducts and, thus, the isolation of the pure complex in high yieldviasimple filtration. ISA has been used for the preparation of polyelectrolyte-surfactant complexes15a,band for complex formation with other charged species such as perylenes or certain dyes,10,15c,16thereby creating highly ordered nanostructured materials with interesting functionalities. In these works, PTCDA was first transformed into the diimides PTCDI by reaction with functionalized amines, followed by a reaction at the introduced functional groups to obtain the ionized PTCDI derivatives, which can be finally complexed with oppositely charged surfactants to produce ISA fu

展开