Controllable Preparation For The Supermolecular Nanostructures Based On Function-oriented Phthalocyanine And Perylene Diimide Groups

Nowadays there have high demands with the functional materials, they should be in lowenergy consumption, little pollution and high value. In our thesis, we have obtained highlyordered nanostructures through self-assembly method, and the principle of the self-assemblyprocess has also been discussed, indicating the effect of the prepare method on tuning theintermolecular interaction and in turn the molecular packing mode in the aggregates ofcompounds. Our research work has been mainly focused on the following four respects:1. Controllable self-assembly of sandwich-type mixed （phthalocyaninato）（porphyrinato） rareearth triple-decker complexesTwo novel sandwich-type mixed （phthalocyaninato）（porphyrinato） rear earth complexesTb2[TClPP]2Pc （1） and Tb₂[TClPP] Pc₂（2） have been fabricated into nanostructures by asolution-based method. Their self-assembly properties have been comparatively studied byelectronic absorption spectroscopy, transmission electron microscope （TEM）, X-raydiffraction （XRD） techniques and current–voltage （I–V） measurements. The self-assembly ofthe two molecules results in totally different morphologies in aggregate: one-dimensionalnanoribbon from1vs two-dimensional nanosheet from2. The electronic absorptionmeasurements indicated that J-type aggregates have been formed with the increasingred-shifted degree from nanoribbons to nanosheets. Examination by XRD revealed that in thenanostructures of compounds1and2, a dimeric supramolecular structure was formed throughan intermolecular π-π interaction and van der Waals between two sandwich-type molecules,which as the building block self-assembles into the target nanostructures. In addition, thenanosheets from2were revealed to show excellent semiconducting properties with theconductivity of3.0×10^-3S·m^-1.2. Solution-processed thin films based on sandwich-type mixed （phthalocyaninato）（porphyrinato） europium triple-deckers and characteristics in ammonia sensingThe solution-processed thin films of a series of three sandwich-type mixed（phthalocyaninato）（porphyrinato） europium complexes1-3were prepared by aquasi-Langmuir-Sh fer （QLS） method. Examination by spectroscopic methods revealed thatJ-type aggregates have been formed with the increasing degree of order of molecular stacking 1<2<3films. The IR and XRD results reveal that, a dimeric supramolecular structure wasformed depending mainly on the π-π interaction between the tetrapyrrole cores of neighboringtriple-decker molecules, which, as the building blocks, self-assembled into the targetnanostructures through intermolecular hydrogen bonds. An increasing sensitivity to NH3atvaried concentrations in the range of15-800ppm, follows the order3<1<2. In particular,excellent sensitivity, nearly complete reversibility and reproducibility to NH3even at roomtemperature are obtained for the ultra-thin solution processed films from2.3. Synthesis of a symmetric substituted perylenetetracarboxylic diimide derivative （EPDI） andthe properties of the resulting EPDI/CdS hybrid systemThe target compound N,N’-bis[3-[1,3-bis[2-（2-methoxyethoxy）ethoxy]-2-propoxy]propyl]-1,7-di（4’-t-buyl）phenoxy-perylene-3,4:9,10-tetracarboxylic diimide （EPDI） wasdesigned and prepared, which was characterized by UV-visible spectrum （UV-vis）、massspectra （MALDI-TOF MS）、HNMR, etc. In particular, the electrochemical property of EPDIhas been evaluated using differential pulse voltammetry （DPV）. And EPDI was transfer toquartz substrate by Langmuir-Sh fer （LS） method, resulting homogeneous films which werecharacterized by UV、X-ray diffraction （XRD） and atomic force microscope （AFM）. Theresult revealed that EPDI molecules stacked in LS films with a face-to-face configuration andedge-on orientation. Furthermore, CdS nanoparticles grew on it in situ, resulting theEPDI-CdS organic-inorganic hybrid films, which were further characterized by UV-visible,fluorescence, AFM and energy-dispersive X-ray spectroscopy （EDS）. In particular, energytransfer from CdS to EPDI has been found in the hybrid films.4. Synthesis and properties of fluorine generation of ethoxy substituted phthalocyanineThree novel phthalocyanine compounds M[Pc（OCH₂CF₃）₈]（M=2H, Zn, Cu） have beendesigned and synthesized successfully. Three compounds prepared were characterized by awide range of methods including UV-visible absorption spectra, infrared spectroscopy,MALDI-TOF mass spectrometry and elemental analysis. The electrochemistry of compoundswas studied by differential pulse voltammetry （DPV） method and the density functionaltheory （DFT） method for the HOMO and LUMO energy level. In particular, a charge-transfer（CT） peak in the UV-Vis spectra of both H₂Pc（OCH₂CF3）8and Cu[Pc（OCH₂CF₃）₈] in THFsolution with a low concentrations（¹0-5mol L-1）. An intermolecular charge-transfer process can be proved by UV-Vis spectra of adding oxidant or reductant in phthalocyanines solutionsand Electrochemical Impedance Spectroscopy measurement. This is a first example forphthalocyanine molecules to exist a spontaneous intermolecular charge transfer in the verydilute solution, which might be valuable to study the charge-transfer behavior of molecules insolution.