The Synthesis And Assembly Properties Of The Crown Ether Substituted Perylene Diimides: Effects Of Metal-ligand Coordination On Tuning The Intermolecular Interaction

Nowadays there are high demands with the functional materials, whichshould be in low energy consumption, little pollution and high value. Fabricatedthe Organic-Inorganic hybrid nanocomposite has caused the scientists’ interest,which is an important direction of the development of the molecular chemistry.The followings are the specific contents of our work:1. Tuning the morphology of self-assembled nanostructures of porphyrinsmolecules by varied meso-substituentsMetal free tetrakis（4-methoxylphenyl）porphyrin （Ⅰ）,tetra（phenyl）porphyrin （Ⅱ） and tetrakis（4-chlorophenyl）porphyrin （Ⅲ） wereassembled into organic nanostructures by “one-step” method. Theirself-assembly properties, especially the effect of meso-substituents with variedelectron-donating withdrawing properties on tuning and controlling themorphology of self-assembled nanostructures of these porphyrin derivatives,have been comparatively studied by electronic absorption, transmissionelectronic microscopy （TEM）, and X-ray diffraction （XRD） techniques. J-typeaggregates have been formed with the increasing degree of intermolecularinteraction （Ⅲ）<（Ⅱ）<（Ⅰ），which are in agreement with the degree ofelectron-donating and electron-withdrawing properties of the meso-substituents.TEM observation suggests that the microcrystal structure is dependent on thedegree of intermolecular interaction resulting from varied meso-substituents of these porphyrin derivatives. Square and lamellar, nanorods as well as nanobeltsstructures have been obtained in aggregates of porphyrin （Ⅰ）,（Ⅱ）,（Ⅲ）,respectively. Favorable growing direction of microstructures in these aggregatesis different in the self-assembly process, which in turn result in differentmorphology for the self-assembled nanostructures.2. Controllable self-assembly of a crown ether functionalizedPerylenetetracarboxylic Diimide: effects of metal–ligand coordination on tuningthe intermolecular interaction, and dimensions of self-assembled nanostructures.A crown ether substituted perylenetetracarboxylic diimide （PDI） derivative,N,N’-di（4’-benzo-15-crown-5-ether）-1,7-di（4-tert-butyl-phenoxy）perylene-3,4;9,10-tetracarboxylic diimide （CRPDI）, has been synthesized and characterized.Dimerization of CRPDI is induced in CHCl₃by addition of K⁺and in methanol,as revealed by absorption and emission spectroscopy. Cofacial dimer formationin the presence of K⁺proceeds in a two-step three-stage process, as indicated byabsorption spectroscopy. The belt-and rope-like nanostructures in the cast filmsfabricated from methanol and CHCl₃solution for addition of K⁺are presentedby SEM, respectively, implying the effect of both cation and solvent on tuningthe intermolecular stacking. Furthermore, the conductivity of the rope-likenanostructures from the cation-induced dimeric species is more than ca.1orderof magnitude higher than belt-like nanostructures from solvent-induced dimericspecies. The present result appears to represent the new effort toward realizationof controlling and tuning the morphology of self-assembled nanostructures of perylenetetracarboxylic diimide derivatives through molecular design andsynthesis. It will be valuable for the design and preparation of PDI-basednano-electronic and nano-optoelectronic devices with good performance due tothe close relationship between the molecular ordering and dimensions ofnanostructures and the performance of nanodevices.3. Controllable self-assembly of a crown ether functionalizedPerylenetetracarboxylic Diimide: effects of different metal–ligand coordinationand solventA novel perylenetetracarboxylic diimide （PDI） derivative,N,N’-di（4’-benzo-18-crown-6-ether）-1,7-di（4-tert-butyl-phenoxy）perylene-3,4;9,10-tetracarboxylic diimide （CRPDI）, has been synthesized and characterized.Dimerization of CRPDI is induced in CHCl₃by addition of K⁺and Rb+, asstudyed by absorption and emission spectroscopy. After added two ions, thefluorescence intensitys were all inhancement, specially, with addition of K⁺, thefluorescence intensity was significantly enhanced, which can be used on“OFF-ON” fluorescent probe. The nanoparticle，two-dimensional sheet structureand nanostructure between nanoparticle and two-dimensional sheet structure inthe cast films fabricated from CHCl₃and CHCl₃solution for addition of K⁺andRb+are presented by SEM, respectively, implying the effect of different cationon tuning the intermolecular stacking. Furthermore, the conductivity of thetwo-dimensional sheet nanostructures from the cation-induced dimeric speciesrise up to6.7S m^-1, implying the ion channel was formed in this aggregates, the conductivity of the cast film from Rb+cation-induced dimeric species is morethan triple higher than nanoparticle structures from CHCl₃.To study the influence of different solvents, a novel perylene diimidederivatives with a hydrophobic long chain and4’-Aminobenzo-18-crown-6,N-（n-hexyl）-N,（4’-benzo-18-crown-6）1,7bis-（tert-butyl-phenoxy）3,4;9,10perylene diimide, PDI（18C6） was designed and synthesized. Three aggregateswere prepared from chloroform, methanol and hexane respectively. There wereall H aggregate as revealed by absorption and emission spectroscopy. Thenanocube，nanostripe and rose petals-like nanostructures in the cast filmsfabricated from CHCl₃,methanol and hexane were presented by SEM,respectively, implying the effect of different solvents on tuning theintermolecular stacking. It will be valuable for the design and preparation ofPDI-based nano-electronic and nano-optoelectronic devices with goodperformance due to the close relationship between the molecular ordering anddimensions of nanostructures and the performance of nanodevices.