The Sandwich-type Rare Earth Metals (tetraaza) Porphyrin, Phthalocyanine Synthesis And Properties Of Complexes,

Porphyrins, along with their artificial analogues tetraazaporphyrins and phthalocyanines, belong to a cyclic tetrapyrrole family in which the four pyrrole or isoindole nitrogen atoms are able to coordinate with a range of metal ions. With large metal centers which favor octa-coordination (e.g. rare earths, actinides), sandwich-type complexes in the form of double- or triple-deckers can be formed. Since the first sandwich-type metal phthalocyaninato double-decker complex was synthesized in 1936, people have contributed much attention to such complexes, and a variety of sandwich-type double- and triple-deckers with porphyrinato and/or phthalocyaninato ligands have been synthesized and researched deeply. Due to the intramolecularπ-πinteractions and the intrinsic nature of the metal centers, these complexes show extraordinary optical, electronic, thermodynamic and magnetic properties, which enable them to be used as materials of novel molecular conductor, molecular magnet, molecular electronics, optical limitation, non-linear optics, gas sensor, electrochromism, opti-electronic transformation and liquid crystal etc..Moreover, photochromic materials are attached much importance to owing to their potential application in the areas of optical memory, information storage, dopes, pigments and other correlative industries. We can use their two forms (open form and closed form) in different colors to record information in binary system. In recent years, it has become a popular field to design and synthesize this kind of materials with novel structures or availing in practice. Among the numerous photochromic compounds, 1,2-diarylethene, especially 1,2-bisthienylethene (BET) derivatives have been regarded as an outstanding type, due to their sufficient thermal stability and very high resistance to photo-fatigue. Researchers have being paid much enthusiasm and energy to synthesize this kind of compounds. On the one hand, they wish to design novel molecular materials with advanced or new features; on the other hand, they expect to meet the needs of practical application.My research work in these fields has been focused on the following respects: 1. Synthesis and spectroscopic characterization of mixed 5,10,15,20-tetrakis(4-chlorophenyl)porphyrinato and l,4,8,ll,15,18,22,25-octakis(1-butyloxy)phthalocyaninato rare earth(III) double-decker complexesReaction of the half-sandwich complexes [RE^III(TClPP)(acac)] [RE = Sm, Eu, Tb, Dy, Y, Ho, Lu; TClPP = meso-tetrakis(4-chlorophenyl)porphyrinate; acac = acetylacetonate], generated in situ from RE(acac)3 ? nH₂O and H₂(TC1PP), with 1,4,8,11,15,18,22,25-octakis(1-butyloxy)phthalocyanine [H₂Pc(α-OC₄H₉)₈] in refluxing n-octanol gave exclusively the protonated mixed (phthalocyaninato)(porphyrinato) rare earth double-deckersHRE^III(TClPP)[Pc(α-OC₄H₉)₈] [RE = Sm, Eu, Tb, Dy, Y, Ho, Lu]. Considering that both neutral mixed (phthalocyaninato)(porphyrinato) rare earth double-deckers RE^III(TClPP)[Pc(α-OC₅H₁₁)₄] (RE = Sm, Eu, Y) and the protonated analogues HM^III(TClPP)[Pc(α-OC₅H₁₁)₄] (RE = Sm, Eu, Y) were isolated from the similar reactions just using H₂[Pc(α-OC₅H₁₁)₄] instead of H₂Pc(α-OC₄H₉)₈, and only neutral analogues [RE^III(TClPP)(Pc)] were isolated in our former work, we noticed thatα-alkoxylation of the phthalocyanine ligand can stabilize the protonated form, which was supported by molecular orbital calculations. These observations clearly showed the importance of the position and number of substituents at the phthalocyanine ligand in controlling the nature of the isolated mixed (phthalocyaninato)(porphyrinato) rare earth double-deckers. The series of protonated complexes HRE^III(TClPP)[Pc(α-OC₄H₉)₈] were characterized by elemental analysis and various spectroscopic methods (MS, NMR, UV-Vis, near-IR, and IR).2. Synthesis and spectroscopic characterization of photochromic half-sndwichand sandwich type rare earth complexes containing tetraazaporphyrinato ligandHalf-sandwich type rare earth tatraazaporphyrinato complexes RE[TAP(C₇H₉S)₈](acac) [RE = Nd, Eu, Y, Ho, Lu; TAP(C₇H₉S)₈ = 2,3,7,8,12,13,17,18-octakis-(2',4',5'-trimethyl -3 '-thienyl)tetraazaporphyrinato] have been prepared by treating 1,2-dicyano-1,2-bis(2',4',5'-trimethyl-3'-thienyl)ethane in the presence of DBU with the corresponding RE(acac)3 ? nH₂O (acac = acetylacetonate) in n-pentanol. And reactions of the half-sandwich type complexes [RE^III(Pc)(acac)] with 1,2-dicyano-1,2-bis(2',4',5'-trimethyl-3'-thienyl)ethane in the presence of DBU in n-pentanol, have led to the isolation of protonated mixed (tetraazaporphyrinato)(phthalocyaninato) rare earth double-deckersHRE[TAP(C₇H₉S)₈](Pc) (RE = Nd, Eu, Y, Ho, Lu). As far as we know, these double-deckers are the first sandwich type compounds mixing tetraazaporphyrinato and phthalocyaninato ligands, as well as the first sandwich-type bisthienylethene derivatives in the photochromic family. We managed to synthysize half-sandwich and sandwich type rare earth complexes containing tetraazaporphyrinato ligand in the ways that we usually prepare phthalocyaninato complexes. So approaches to synthesize tetraazaporphyrinato compounds have been increased. These complexes were characterized by elemental analysis and various spectroscopic methods (MS, NMR, UV-Vis, and IR). And we researched the photochromic feature of these compounds in detail.