Synthesis, Characterization And Properties Of New Type Porphyrin And Phthalocyanine Complexes

With the development of science and technology,the investigation and application of new functional materials have been the main task for production and life.People are pursuing for discovering and developing new functional man-made systems that can competent with the natural systems.After having known the significance of the porphyrins and their derivatives involved in the most important processes of natural lives,the structures,properties,and functions of the porphyrin complexes have always been the key points of the research work and discussion.Phthalocyaninato complexes,a kind of compounds that have the same structures with those of porphyrins,which are widely used as industral commodities from their first discovery in the beginning of last century,have triggered wide interests in developing their catalistic and photo-electric properties as the new functional materials recently.The tetrapyrrolic macrocyclic molecules such as porphyrin and phthalocyanine with unique photonic,electronic,and magnetic properties as well as their stabilites in air deduced from their particular structures,have attracted a lot of researchers devoting themselves to this field.Most of the work involves the modification and assembling of the macrocycles.Preparation of the porphyrinato and/or(na)phthalocyaninato sandwich-type complexes is one kind of useful method among them.Two or three porphyrin and/or (na)phthalocyanine ligands are coordinated with one or two rare earth metal ions to form the highly conjugated sandwich type double- or triple-decker complexes.StrongÏ€-Ï€interactions between the maerocyeles induces remarkable physical and chemical properties of these complexes,therefore,to provide anticipated candidates as molecular semiconductor,photo conductor,optical materials,optical limiting,non-linear optical materials,gas sensors,electrochromic materials,molecular magnetics,and liquid crystal materials.During the past several years,our research group had paid our attention to synthesize the porphyrin and phthalocyanine rare earth sandwich complexes.On one hand,we have been aiming to develop effective synthetic routes and methods towards preparing the porphyrin and phthalocyanine ligands with different peripheral substitutes,on the other hand to exploit the physic-chemial properties,organic field effect transistor(OFET)functionalities, and supramolecular assembling nature.With our continuous efforts,we have prepared a series of symmetrical and unsymmetrical sandwich-type double- and triple-decker complexes.In this dissertation,our research work has been focused on the following respects: 1.Bis(phthalocyaninato)europium(â…¢)double-decker complexes and phthalocyaninato copper(â…¡)complexes fused with different number of 15-crown-5 moieties:synthesis, spectroscopy,supramolecular structures,and the effects of substituent number and molecular symmetryThe design and preparation of supramolecular structures,which have been inspired by the significant progress in biological science and the many important potential applications in material science and molecular electronics,are great challenges for chemists and material scientists.Phthalocyanine has been an important class of dyes and pigments since their fast synthesis early last century.In particular,bis(phthalocyaninato)rare earth complexes have been intensively studied as advanced materials for gas sensors, electrochromic displays,photoconductors,and molecular electronics.On the other hand, crown ethers that have remarkable recognition and metal binding properties have been found wide applications also in molecular electronic devices.The combination of these two functional subunits for the purpose of constructing novel supramolecular structures with new and multi-functional properties has stimulated wide research interest.In this paper,we reported the synthesis,spectroscopy,supramolecular structures of a series of heteroleptic bis(phthalocyaninato)europium(â…¢)complexes with one,two,three, and four 15-crown-5 voids attached at different positions of one of the two phthalocyaninato ligands:Eu(Pc)(Pc')[Pc'= Pc(15C5),Pc(opp-15C5)₂,Pc(adj-15C5)₂, Pc(15C5)₃,Pc(15C5)₄];The other series of phthalocyaninato copper compounds CuPc(15C5)n(n = 1-4)is also been prepared employing a novel methodology using heteroleptic bis(phthalocyaninato)rare earth complexes Eu(Pc)(Pc')[Pc' = Pc(15C5), Pc(opp-15C5)₂,Pc(adj-15C5)₂,Pc(15C5)₃,Pc(15C5)₄]as starting material,reaction with copper acetate in large excess amount provides two different kinds of phthalocyaninato copper compounds Cu(Pc)and CuPc(15C5)_n(n = 1-4)in relatively good yields.Having a series of closely related phthalocyanines with different number and / or disposition of 15-crown-5 groups at the peripheral positions,the effects of 15-crown-5 substituent number and molecular symmetry on the electronic absorption spectra,infra-red(IR) spectra,and supramolecular structure formation induced by K⁺ ions have been investigated.Systematic studies over the formation of dimeric supramolecular structures of the series of monomers reveal and confirm the previously proposed two-step three-stage process of K⁺-induced dimerization of phthalocyanines with three or four 15-crown-5 moieties.2.Synthesis,characterization and third-order nonlinear optical property of novel ethynyl linked heteropentamer composed of four porphyrins and one pyreneOrganic materials,in particular,with the structure of extensively delocalized z-electrons have received significant attention recently due to their large NLO susceptibilities, architectural flexibility,and ease of fabrication.Since porphyrins are promising candidates for nonlinear optical materials in view of not only largeÏ€-conjugated systems but also versatile functionalization at the peripheral positions and various possibilities of the central metalion,the expansion of theÏ€-electronic network of porphyrins has been attempted previously,some porphyrin arrays which were linked by alkyne linkages or directly linked and self-assembled porphyrin oligomers have showed enhanced NLO properties.However, covalently alkyne-linked porphyrin arrays with star shaped arrangement have never been studied on their nonlinear optical properties.In fact,effective and simple synthetic pathway to alkyne-linked porphyrin arrays with well-defined arrangement has attracted great attention for many researchers.In this paper,we used Pd-mediated reactions to join iodo/ethynyl-substituted porphyrin building blocks,synthesizing novel multi-porphyrins-pyrene arrays with a star arrangement, in which four meso-tetraphenyl porphyrins were linked to the center unit of pyrene by four aeetylenyl bonds.Then we investigated their third-order nonlinear optical properties using the Z-scan method with 1064 nm laser pulses of 20 ps duration in comparison with corresponding porphyrin and pyrene monomers.3.Synthesis,spectroscopy,electrochemistry,and photophysical properties of novel sandwich europium(â…¢)complexes with porphyrin ligand beating four pyrenyl groups at the meso-positionsOwing to their unique optical,electrical and magnetic properties associated with the intriguing inter-ringÏ€-Ï€interactions,sandwich-type bis(phthalocyaninato)rare earth complexes have been intensively studied over the past several decades as prospective molecular electronic,molecular magnetic,electrochemical display,and non-linear optical materials.Recently,mixed(phthalocyaninato)(porphyrinato)rare earth analogues have received increasing attention partly because the individual chromophores display very different optical and redox properties which facilitate the study of theÏ€-Ï€interactions and the extent of hole delocalization.The mixed ring triple-decker complexes are also attractive for their potential use in information storage due to their large number of redox states,reversible electrochemistry,and relatively low oxidation potentials.It is well known that to tune the performance of the sandwich compounds,a good method is to introduce effective substituents onto porphyrin or phthalocyanine ring.In this paper,we devised and synthesized a novel porphyrin ligand with four pyrenyl groups at the meso-positions H2TPYRP,with which the mixed(phthalocyaninato)(porphyrinato) europium double- and triple-decker complexes Eu(Pc)(TPYRP)and Eu₂(Pc)₂(TPYRP) were prepared according to published procedure.To the best of our knowledge,these represent the first example of sandwich tetrapyrrole rare earth complexes attached directly with the excellent pyrenyl fluorophores.As a result,their photophysical properties were comparatively studied together with that for the monomeric metal free porphyrin H₂TPYRP.