Design,synthesis And Semiconduct Properties Of The Self-assembled Orderly-structure Based On Phthalocyanine / Porphyrinato Metal Complexes

Sandwich phthalocyaninato and/or porphyrinato metal complexes have attracted increasing research interest in areas of molecular devices because of their unique optical and electronic properties associated with the extended p networks along the axis perpendicular to the macrocycle planes. Meanwhile,based on their unique,electrical,and magnetic properties, it has many position for substituent group to adjust their properties. In the various resch directions self assembly and OFETs are always important point.Our research work has been focused on the following respects: 1.(TFPP)Eu[Pc(OPh)8]2/CuPc Two-Component Bilayer Heterojunction-Based OrganicTransistors with High Ambipolar PerformanceOrganic thin film transistor(OTFT) devices fabricated by the solution-based QLS technique from a mixed(phthalocyaninato)(porphyrinato) europium complex(TFPP)Eu2[Pc(OPh)8]2 exhibit air-stable ambipolar performance with mobilities of 6.0 × 10-5 for holes and 1.4 × 10-4 cm2 V-1 s-1 for electrons, respectively. In good contrast, the two-component bilayer heterojunction thin film devices constructed by directly growing(TFPP)Eu2[Pc(OPh)8]2 on vacuum deposited(VCD) CuPc film using solution based QLS method were revealed to show unprecedented ambipolar performance with carrier mobilities of 0.16 cm2 V-1 s-1 for holes and 0.30 cm2 V-1 s-1 for electrons. In addition to the intrinsic role of p-type organic semiconductor, the VCD CuPc film on the substrate also acts as a good template that induces significant improvement over the molecular ordering of triple-decker compound in the film. In particular, it results in the change in the aggregation mode of(TFPP)Eu2[Pc(OPh)8]2 from J-type in the single-layer film to H-type in the bilayer film according to the UV-vis, XRD and AFM observations. 2. Design, Synthesis, Aggregation Behavior of Sandwich Mixed(Phthalocyaninato)(Porphyrinato) Europium Triple-Deckers. Effect of Substituent on Tuning the Intermolecular InteractionTwo new sandwich mixed(phthalocyaninato)(porphyrinato) europium triple-decker(TDMAPP)Eu2[Pc(OPh)8]2(1) and(TPyP)Eu2[Pc(OPh)8]2(2) [TDMAPP = dianion of 5,10,15,20-tetrakis(4-N,N-dimethylaminophenyl) porphyrin; TPyP = dianion of 5,10,15,20-tetrakis(4-pyridyl) porphyrin; Pc(OPh)8= dianion of 2,3,9,10,16,17,23,24-octa(phenoxy) phthalocyanine], were designed and synthesized. The self-assembled aggregates of 1 and 2 were fabricated by means of a solution-based quasi-Langmuir–Sh?fer(QLS) method. Both structures and properties of the aggregates of 1-2 were comparatively studied by UV-vis absorption spectroscopy, atomic force microscopy(AFM), X-ray diffraction(XRD) techniques and current–voltage(I–V) measurements. Experimental results indicated the molecules of 1 in the self-assembled aggregates adopted a typical J-type(edge-to-edge) aggregation mode, whereas those of 2 took a ―face-to-face‖ conformation and ―edge-on‖ orientation, implying the effect of side-group substituents on tuning the intermolecular stacking. XRD and AFM characterization clearly showed evidence for the formation of highly textured film structures with controlled molecular orientations within the self-assembled aggregates of 1, while a dimeric supramolecular structure was revealed and thus as the building block self-assembles into the target the net-like nanostructures for the aggregates of 2. In addition, the highly ordered film of 1 showed good semiconducting property with a conductivity of ca 2.35×10-5 S·cm-1, which is more than ca. 1 order of magnitude higher those of 2, closely related to micro-structures and morphology found for the self-assembled aggregates.