Unmasking the chemistry and properties of non-peripherally octasubstituted phthalocyanines

摘要: The paper reviews the development of chemistry, properties and applications 1,4,8,11,15,18,22,25- (or non-peripheral) octasubstituted phthalocyanines that has been undertaken at University East Anglia over last quarter a century. research proved valuable for initiating developing number areas phthalocyanine science, not least because compounds exhibit seldom shared by Pc derivatives with other substitution patterns. In particular are obtained isomerically pure substituents' location non-peripheral sites as opposed to peripheral positions ensures superior solubility lower aggregation in most hydrophobic solvents. A further significant difference between isomeric (np)- (p)-octasubstituted is effect substituents on energy Q-band, those former leading more bathochromic shifts this absorption band into near infra-red. Examples np-octasubstituted columnar mesophase behavior, property their p-octasubstituted counterparts. favorable compounds, including examples which one four benzenoid rings bears different from three (so called AAAB structures), organic solvents facilitates deposition thin film formulations. high degree molecular organisation within Langmuir-Blodgett (LB) films amphiphilic investigated using various methods. Spin-coated certain AAAA series have shown contain layer structuring purpose designed used formation self-assembled monolayers (SAMs). use LB spin-coated electrical devices described. Various SAMs deposited gold surfaces explored gas sensing. Recent attention focused use, when onto nanoparticles, PDT, an approach complementing conventional PDT studies. principal challenge obtaining preparing precursor phthalonitriles. Though 3,6-dialkoxyphthalonitriles readily prepared, early access 3,6-dialkylphthalonitriles was somewhat laborious. However, convenient syntheses latter now available through metal catalyzed cross-coupling reactions. Interesting contrasts reactivity 4,5-dialkylphthalonitriles uncovered. Thus reactions excess lithium alcoholic or MeMgBr provide particularly ready macrocycles hybrids tetrabenzoporphyrin structures. This level very among 4,5-dialkylphthalonitriles. Unexpectedly limited np-octahexylsubstituted Si(OH)2Pc condensation exploited basis stepwise construction m-oxo linked hetero-chromophore arrays. Finally, unexpected novel EPR active Cd2Pc3 complexes both np- p-octaalkyl substituted CdPcs provided where behaved similarly – contrast behavior exhibited alternatively date.