Design, Synthesis, Crystal Structure And Luminescence Properties Of Novel Porphyrin And Phthalocyanine Supramolecular Complexes

Metalloporphyrin and phthalocyanine complexes had been widely used in optical materials, catalytic agents, chemical sensor, solar battery, fluorescent probe, photosensitizer and other fields, owing to their intriguing thermal stability, light stability and the larger visible extinction coefficients, etc. In this paper, by using Zn(Ⅱ) meso-tetraphenylporphine and Zn(Ⅱ) phthalocyanine as the building blocks, a series of novel porphrin and phthalocyanine supramolecular complexes have been synthesized via the non-covalent bonding. Furthermore, the relationship among composition-structure-performance were investigated. It laid the foundation for the development of novel functional materials. According to some creative results, they were outlined as follows:1. Owing to the fact that4,4’-bipyridine and terpyridine derivatives possessed good coordination ability and characteristic of the adjustable coordination. A series of novel porphyrin and phthalocyanine supramolecular complexes(ZnTPP)2-(dpe)-(MB)2(1)(ZnTPP=Zn(Ⅱ) meso-tetraphenylporphyrin, dpe=1,2-Di(4-pyridyl)ethylene, MB=methylbenzene),(ZnTPP)2·(4-bpyo)·(CB)4(2)(4-bpyo=N,N’-Bis-pyridin-4-ylmethyl-oxalamide, CB=chlorobenzene),(ZnTPP)2·(3-bpyo)·(DCE)2·(H2O)4(3)(3-bpyo=N,N’-Bis-pyridin-4-ylmethyl-oxalamide, DCE=1,2-chlorethane),(ZnPC)2·(3-bpyo)·(DMF)4(4)(ZnPC=Zn(Ⅱ) phthalocyanine, DMF=N,N’-two methyl formamide),(ZnTPP)2·(4-btapa)·(DMF)(5)(4-btapa=N,N’,N"-tris(4-pyridyl)trimesic amide) have been synthesized through the coordination of organic ligands with Zn(Ⅱ) meso-tetraphenylporphine and Zn(Ⅱ) phthalocyanine. Their structures and properties have been also characterized by X-ray single crystal diffraction and fluorescence spectrometer, etc. The relationships among their composition-structure-performance have been studied. In addition, the results have indicated that the conformation of the ligands and the number of coordination sites play an important role on the supramolecular assembly structure. Meanwhile, the luminescence properties of porphyrin and phthalocyanine supramolecular complexes with different frameworks were further investigated.2. Based on the multi-ligand model characteristics for the oxygen atom, a series of organic ligands containing oxygen atom were designed and synthesized. Through the axial coordination of oxygen atom with the central metal ion of Zn(II) meso-tetraphenylporphine, a series of novel porphyrin supramolecular complexes(ZnTPP)·(pdo)·(NB)(6)(pdo=pyridine N-oxide, NB=Nitrobenzene),(ZnTPP)2·(bpdo)-(DCE)2(7)(bpdo=4,4’-bipyridine N-oxide, DCE=1,2-chlorethane),(ZnTPP)·(DO)2(8)(DO=1,4-Dioxane),(ZnTPP)·(THF)2(9)(THF=Tetrahydrofuran),(ZnTPP)·(CYC)2(10)(CYC=Cyclohexanone) were synthesized via the non-covalent bonds. The relationship among composition-structure-performance of these supramolecular complexes has been studied. The results have shown that the coordination mode of oxygen atom was different from that of nitrogen atom. The ligand containing oxygen atom can lead to multiple-coordinational assembly of porphyrin supramolecular complexes. Additionally, luminescence and catalytic properties of this kind of supramolecular complexes have been studied.3. With the prone photoisomerization and light response, the azobenzene with a chromophore had been widely used in the synthesis of the optical materials. Two functional molecules have been selected as ligands and two novel porphyrin supramolecular complexes (ZnTPP)2·(apd)·(MB)(11)(apd=4,4’-azopyridine, MB=methylbenzene),(ZnTPP)2·(dpds)(H2O)4(12)(dpds=4,4’-Dipyridyl disulfide) have been synthesized. Then, their assembly behaviors and luminescence properties have been investigated.4. Based on specific structure and light-to-electric energy conversions of naphthalimide and perylenediimide ligands, two functional molecule ligands have been designed and synthesized, and both a porphyrin supramolecular complex (ZnTPP)2·(NTCDI)·(DMF)4(13)(NTCDI=Naphthalene-1,4,5,8-tetracarboxylic Dianhydride) and phthalocyanine supramolecular complex (ZnPC)2·(NTCDI)(14) were prepared and synthesized. Their single crystal structures and spectral characteristics were also characterized. At the same time, the potential advantages and characteristics of functional molecular groups have been further expored in the assembly of functional supramolecular structures combined with the assembly strategy of crystal engineering, which will open up new avenues for the further development of new photoelectric functional materials.