Perfluorinated Porphyrazines. 5. Perfluoro-a,b-dicyanostylbene: Molecular Structure and Derived (Sub)Porphyrazine Complexes with IIIa Group Elements

Abstract

Template cyclomerization of perfluoro-a,b-dicyanostylbene in the presence of trichlorides of IIIa group elements results in formation of pentafluorophenyl substituted boron(III) subpophyrazinate ([(Cl)BsPAF 30 ]) and aluminum(III) and gallium(III) porphyrazinates ([(Cl)MPAF 40 ], M=Al, Ga). Their spectral-luminescence properties are discussed, revealing blue shift of the Q-band and brighter fluorescence comparatively to non-fluorinated analogues. In addition, the molecular structure of trans-perfluoro-a,b-dicyanostylbene was determined by single crystal X-ray diffraction.

Recent advances in subphthalocyanines and related subporphyrinoids

“…This hypothesis has recently been reinforced through the reaction of a cis/trans -mixture of the perfluorinated bisaryl dinitrile with BCl 3 in p -xylene, which leads to SubPz 249 and recovery of the unreacted fumaric isomer. 514…”

“…This hypothesis has recently been reinforced through the reaction of a cis/trans-mixture of the perfluorinated bisaryl dinitrile with BCl 3 in p-xylene, which leads to SubPz 249 and recovery of the unreacted fumaric isomer. 514 Apart from the perfluorinated SubPz 249, other hexaaryl-SubPzs (255-267) have not been prepared directly from a cyclotrimerization reaction, because the corresponding bisaryl maleonitrile precursors are difficult to prepare. In these cases, the thermodynamically more favoured fumaronitrile isomers are obtained as the main, or sometimes exclusive products.…”

The p-Metal Porphyrins: from Specificity of Properties to Application in Medicine, Catalysis, and Optoelectronics

“…Perfluorination of phenyl rings in [ClBsPAF 30 ] leads, on the contrary, to the disappearance of the band at 394 nm observed in the spectrum of initial boron(III) complex. [32] The same effect is observed in the case of indium(III) octaphenylporphyrazine. [6] An unprecedented type of UV-vis absorption spectrum, which combined stable main group porphyrin complexes with transition d-metal complexes by its uni-formity, was discovered for the first time in the work [88] and received further interpretation.…”

“…The synthesis of main group porphyrin complexes is usually the reaction of halides/acetates with free porphyrin (for example [28] or SM, Table S4) or template assembly using nitrile as in the case of boron subphthalocyanines/ subporphyrazines. [6,17,30,32] The tellurium porphyrin complex was prepared by treatment of TeCl 4 with dilithio mesotetra(p-tolyl)porphyrin. [46] The synthesis using an organometalic derivatives as AlAlk 3 is described.…”

“…[30] The boron(III) complexes with tri-and tetrapyrrole analogs of porphyrins are also studied. [31,32] The second exception is Pb, the complexes of which demonstrate the composition of MP without axial anionic ligands as well as the ones of X 2 PbP (X is monoanion). [33,34] Bi(por)(X) (por is TPP or 5,10,15,20-tetra-p-chlorophenylporphine, X is NO 3 , Cl, Br, or I) formed by the central ion in the low oxidation state (+3) crystallize as doubly bridged through Cl or Br centrosymmetric dimers.…”