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Control electronic or excitonic interactions or manipulation electronic current in conjugated pi-system are important and difficult,and which is a key step to produce new materials.How to construction of Porphyrin arrays and preparation of new porphyrinoids efficiently are very important in porphyrin chemistry.Usually,unique structure comes out with special properties.Porphyrinoids have been extensively explored as synthetic models of photosynthetic antenna and functional hosts possing convergent multi-dentate coordination sites.Multipyrrolic macrocycles with the change of the meso carbon and pyrrole unit exhibit different structures and fascinating properties.Highly conjugated multi-porphyrin arrays have received much attention in light of their potential applications in optoelectronic devices,sensors,photovoltaic devices,non-linear optical(NLO)materials,photodynamic therapy(PDT)pigments,and light-harvesting models.The manipulation of interporphyrinic interaction is often essential to achieve desirable electronic and photophysical properties.Palladium catalyzed cross coupling of borylated porphyrins and aryl halides,it is widely used to synthesize some porphyrin arrays which could not be obtained in other strategies.We have successfully synthesized 2,5-thienylene/pyrrolyene bridged β-to-β porphyrin nanorings,2,6-pyridylene-bridged β-to-β porphyrin nanorings,β-to-β terpyridylene/azobenzene bridged porphyrin nanorings,meso-to-meso azobenzene/2,5-pyrrolyene bridged porphyrin nanorings,directly Pd(Ⅱ)-bridged porphyrin belts,porphyrin barrel,and meso,meso-porphyrinic bridged β-to-β porphyrin nanorings by this way,and β-to-β spacer-free porphyrin arrays were also constructed recently in our lab.Although the borylated porphyrins are almost able to react with any aryl halides bought from market,we found it is difficult to synthesis some elegant porphyrin arrays.How to increase the dissolubility and prepare the building blocks are challenges for construction of elagant multiporphyrin arrays.Some new porphyrin arrays recently have been synthesized through Pd-catalyzed cross-coupling reactions or aldehyde condensation and oxidation in our group with suitable precusor.Some new porphyrinoids have also been explored including earring porphyrins and smaragdyrins.Smargdyrin is a historic and puzzling molecule,as its discovery was reported along with sapphyrin by Woodward early in 1966,but its synthesis has not been accomplished so far.Our group reported the first synthesis of earring porphyrins and meso-trimesityl [20]smaragdyrin as a stable antiaromatic compound under ambient conditions.Our synthetic strategy involves a double SNAr reaction of 1,9-dibromo-5-mesityldipyrrin 1 with 5,10-dimesityltripyrran 2 as a key step.Both precursors 1 and 2 were prepared according to the reported methods from our group.After extensive experimentations,we found that refluxing of an equimolar mixture of 1 and 2 in p-xylene in the presence of Cs2CO3 for 48 h gave [22]smaragdrin BF2 complex 3 in 13%yield.To the best of our knowledge,this is the first example of the synthesis of expanded porphyrins by SNAr reaction of tripyrrane anion.Antiaromatic compound 5 is very stable but aromatic compound 6 is easy to be oxidated in air.Neo-confused smaragdyrin were also synthesized in good yield.