182575-04-8Relevant articles and documents
Direct Access to Axially Substituted Subphthalocyanines from Trimethylsilyl-Protected Nucleophiles
Guilleme, Julia,Martínez-Fernández, Lara,Corral, Inés,Yá?ez, Manuel,González-Rodríguez, David,Torres, Tomas
, p. 4722 - 4725 (2015)
A new synthetic one-step approach to perform the axial ligand exchange reaction in subphthalocyanines that employs trimethylsilyl-protected nucleophiles as starting materials is reported. Theoretical calculations indicate that the exchange reaction procee
Synthesis of Meso-Substituted Subphthalocyanine-Subporphyrin Hybrids: Boron Subtribenzodiazaporphyrins
Remiro-Buenama?ana, Sonia,Díaz-Moscoso, Alejandro,Hughes, David L.,Bochmann, Manfred,Tizzard, Graham J.,Coles, Simon J.,Cammidge, Andrew N.
, p. 7510 - 7514 (2015)
The first syntheses of hybrid structures that lie between subphthalocyanines and subporphyrins are reported. The versatile single-step synthetic method uses a preformed aminoisoindolene to provide the bridging methine unit and its substituent while trialkoxyborates simultaneously act as Lewis acid, template, and provider of the apical substituent. The selection of each component therefore allows for the controlled formation of diverse, differentially functionalized systems. The new hybrids are isolated as robust, pure materials that display intense absorption and emission in the mid-visible region. The new compounds are further characterized in solution and solid state by variable-temperature NMR spectroscopy and X-ray crystallography, respectively.
Aluminum chloride activation of chloro-boronsubphthalocyanine: A rapid and flexible method for axial functionalization with an expanded set of nucleophiles
Morse, Graham E.,Bender, Timothy P.
experimental part, p. 6460 - 6467 (2012/09/07)
We have developed a process whereby chloro-boronsubphthalocyanine (Cl-BsubPc) and other BsubPcs are activated to reaction with oxygen, sulfur, and nitrogen based nucleophiles by treatment with aluminum chloride under mild conditions. This allows for the scope of atoms chemically bound to the boron atom to be expanded beyond those derived from the traditional oxygen and carbon based nucleophiles. The successful formation of thiophenoxy and phenylamino derivatives of BsubPc was confirmed spectroscopically and by X-ray crystallography of single crystals. We have proposed a detailed mechanism for this process based on experimental observation and NMR spectroscopy ( 1H, 11B, and 27Al) which involves formation of a complex between a halo-BsubPc and AlCl3 (which we denote BsubPc(Cl) ·Al(Cl′)3). Our observations indicate that the action of phenol on BsubPc(Cl) ·Al(Cl′)3 does not involve direct reaction at the boron atom; rather phenol first reacts at the aluminum atom along the way to the formation of a new intermediate complex BsubPc(OPh) ·Al(O′Ph)3. The consequence is that the rate of this process is independent of the nature of the starting BsubPc. Cl-BsubPc and Br-BsubPc as well as BsubPcs with peripheral substitutents all react to form their respective phenoxy derivatives at the same rate. Quenching of BsubPc(OPh) ·Al(O′Ph)3 with a Lewis base ultimately produces a new bond between the phenol nucleophile and the boron atom of the BsubPc.
