The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies

The synthesis of a range of brominated-B_n-containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr₃ with appropriately substituted alkynes via a bromoboration/electrophilic C–H borylation sequence. The brominated-B_n-PAHs were isolated as either the borinic acids or B-mesityl-protected derivatives, with the latter having extremely deep LUMOs for the B₂-doped PAHs (with one example having a reduction potential of E_1/2 = −0.96 V versus Fc⁺/Fc, Fc = ferrocene). Mechanistic studies revealed the reaction sequence proceeds by initial alkyne 1,1-bromoboration. 1,1-Bromoboration also was applied to access a number of unprecedented 1-bromo-2,2-diaryl substituted vinylboronate esters directly from internal alkynes. Bromoboration/C–H borylation installs useful C–Br units onto the B_n-PAHs, which were utilised in Negishi coupling reactions, including for the installation of two triarylamine donor (D) groups onto a B₂-PAH. The resultant D–A–D molecule has a low optical gap with an absorption onset at 750 nm and emission centered at 810 nm in the solid state.

The synthesis of a range of brominated-B_n-containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr₃ with appropriately substituted alkynes via a bromoboration/electrophilic C–H borylation sequence.     

Pinchings and Norms of Scaled Triangular Matrices

Suppose U is an upper-triangular matrix, and D a nonsingular diagonal matrix whose diagonal entries appear in nondescending order of magnitude down the diagonal. It is proved that $$\|D^{-1}UD\|\ge\|U\|$$ for any matrix norm that is reduced by a pinching. In addition to known examples -weakly unitarily invariant norms - we show that any matrix norm defined by $$\| A \|^{\underline{\underline {{\rm def}}} } \mathop {\max }\limits_{x \ne 0,y \ne 0} {{{\mathop{\rm Re}\nolimits} (x^*Ay)} \over {\phi (x)\psi (y)}},$$ where θ (.) and y (.) are two absolute vector norms, has this property. This includes l p operator norms as a special case.