Crystal Structures, Reaction Rates, and Selected Physical Properties of Halo-Boronsubphthalocyanines (Halo = Fluoride, Chloride, and Bromide)

Abstract

The physical properties, including the solid state arrangement, photophysics, solubility, and electrochemical behavior of a series of halo-BsubPcs (halo = F, Cl, Br) have been measured (IUPAC name halo-(7,12:14,19-diimino-21,5-nitrilo-5H-tribenzo(c,h,m)(1,6,11)triazacyclopentadecinato)-boron(III)). We have found that across the series all are relatively similar in most regards. Exceptions include that F-BsubPc can be 5 to 25 times more soluble than Cl-BsubPc in common organic solvents. F-BsubPc was also found to be hydrolytically stable under the conditions tested, whereas Cl-BsubPc and Br-BsubPc readily hydrolyzed to form HO-BsubPc. The relative rates of reaction for the series of halo-BsubPcs under standard phenoxylation conditions have also been measured. It was found that F-BsubPc does not undergo phenoxylation, whereas Br-BsubPc showed a markedly higher reaction rate relative to Cl-BsubPc. Based on these data some assumptions can be made as to the suitability of either F-BsubPc or Br-BsubPc to be used in place of the more common Cl-BsubPc. The data indicate that F-BsubPc is a potential replacement for Cl-BsubPc in organic electronic materials whereas Br-BsubPc might be more suitable as a chemical intermediate. Comments on the synthetic methods used to produce each halo-BsubPc are also made.

Low-Symmetry Mixed Fluorinated Subphthalocyanines as Fluorescence Imaging Probes in MDA-MB-231 Breast Tumor Cells

“…The ring system is conical in shape with an apical central boron with an axial ligand, usually a halogen ( X = F, Cl, Br) [4], making these macrocycles more polar and less aggregative than their planar tetrapyrrole phthalocyanine (Pc) cousins. Like Pcs, SPcs are synthesized by the templated cyclization of phthalonitrile derivatives.…”

Evaluating Thiophene Electron‐Donor Layers for the Rapid Assessment of Boron Subphthalocyanines as Electron Acceptors in Organic Photovoltaics: Solution or Vacuum Deposition?

“…[1,2] Recently,a no verall efficiency of 4.69 %h as been achieved by using BsubPc chloride (Cl-BsubPc;F igure 1a) as an electron acceptorw hen paired with sexithiophene (a-6T,F igure 1a). [5][6][7][8][9][10][11][12][13][14] For the most part, the derivatives we have synthesized are amenable to vacuum processing and fabricationi nto OPVs by sublimation. [4] Our laboratory has been interested in the synthesis of new BsubPc derivatives for some time now.…”

“…[4] Our laboratory has been interested in the synthesis of new BsubPc derivatives for some time now. [5][6][7][8][9][10][11][12][13][14] For the most part, the derivatives we have synthesized are amenable to vacuum processing and fabricationi nto OPVs by sublimation. For ex-ample,w eh ave recently shown that ad erivativeo ther than Cl-BsubPc, pentafluorophenoxy BsubPc( F 5 -BsubPc), can function within ap lanar heterojunction OPV as either an electron-acceptor or electron-donor material.…”

From chloro to fluoro, expanding the role of aluminum phthalocyanine in organic photovoltaic devices

“…For example, chloro aluminum Pc (Cl-AlPc) has been paired with C 60 for the fabrication of a planar heterojunction (PHJ) and blended organic photovoltaic (OPV) devices. [11][12][13][14] Moving one level down on the periodic table, and given the successful use of Cl-AlPc in OPV devices [5][6][7][8] we decided to look at the effect of substituting the axial chloride of Cl-AlPc with a fluoride and incorporate fluoro aluminum Pc (F-AlPc) into simple PHJ OPV devices. 10 Our group has recently been studying the incorporation of fluorine groups into boron subphthalocyanine (a sub-class of Pcs) which resulted in a decreases in sublimation temperature, a change in the solid-state arrangement (crystal structure) and a change in electrochemical properties.…”