Observations regarding the crystal structures of non-halogenated phenoxyboronsubphthalocyanines having para substituents on the phenoxy group

Abstract

We report the synthesis and systematic description of a series of five para-substituted phenoxy-BsubPcs including their characterization in the crystal state. The nature of the substituents on the phenoxy molecular fragment was chosen so as to vary both the size and electronegativity: specifically with increasingly bulky para-alkyl groups from hydrogen to tert-octyl and a single electronegative substitute (F). Examination of the arrangement of the phenoxy-BsubPcs within single crystals allows us to place each into one of the two categories. The first, which contains all but one of the derivatives, has a repeating motif which is made up of dimers of the BsubPc molecular fragments. The second, containing only the derivative possessing the large tert-octyl substituent, is characterized by the formation of ribbons instead of dimers of the BsubPc fragment. Regardless of motif the arrangement of the BsubPc molecular fragments was found to be convace-concave.

One Well-Placed Methyl Group Increases the Solubility of Phenoxy Boronsubphthalocyanine Two Orders of Magnitude

“…Each structure shows the same close packed pairs of molecules (dimers), which we have previously noted as a common packing motif for phenoxylated BsubPcs, including phenoxyBsubPc and 4-methylphenoxy-BsubPc. 28 According to the metrics we have previously established 28 a direct quantitative comparison of this packing structure shows that the spacing of the molecules in all of the solvent-free crystal structures varies only slightly ( Table 1). The molecules making up the close packed pairs are the same distance apart (as indicated by the B−B d 1 and C g to C g distances) in each arrangement, with the boron−boron (d 1 ) distance between the closest molecules in different pairs ranging between 5.576(3) Å and 7.011(4) Å for phenoxy-BsubPc and compound 2a, respectively.…”

The mixed alloyed chemical composition of chloro-(chloro)n-boron subnaphthalocyanines dictates their physical properties and performance in organic photovoltaic devices

“…4 BsubPcs are known to be aromatic, non-planar, and cone-shaped molecules. [5][6][7][8] Despite being rst synthesized and characterized in the early 1970s, the majority of the synthesis and application work on BsubPcs has been carried out within the last 10 to 15 years. [9][10][11][12] Halo-BsubPcs are relatively easy to prepare by the reaction of phthalonitrile (an ortho-dinitrile) with a boron trihalide templating agent such as BCl 3 (ref.…”

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.…”