9,10-Dihydro-9,10-diboraanthracene (DBA) provides a versatile scaffold for the development
of boron-doped organic luminophores. Symmetrically C-halogenated DBAs are obtained
through the condensation of 4-bromo-1,2-bis(trimethylsilyl)benzene or 4,5-dichloro-1,2-bis(trimethylsilyl)benzene
with BBr3 in hexane. Unsymmetrically C-halogenated DBAs are formed via an electrophilic
solvent activation reaction if the synthesis is carried out in o-xylene. Mechanistic
insight has been achieved by in situ NMR spectroscopy, which revealed C-halogenated
1,2-bis(dibromoboryl)benzenes to be the key intermediates. Treatment of the primary
9,10-dibromo-DBAs with MesMgBr yields air- and water-stable C-halogenated 9,10-dimesityl-DBAs
(2-Br-6,7-Me2-DBA(Mes)2; 2,6-Br2-DBA(Mes)2; 2,3-Cl2-6,7-Me2-DBA(Mes)2; 2,3,6,7-Cl4-DBA(Mes)2).
Subsequent Stille-type C-C-coupling reactions give access to corresponding phenyl,
2-thienyl, and p-N,N-diphenylaminophenyl derivatives, which act as highly emissive
donor-acceptor dyads or donor-acceptor-donor triads both in solution and in the solid
state. 2-Thienyl was chosen as a model substituent to show that already a variation
of the number and/or the positional distribution of the donor groups suffices to tune
the emission wavelength of the resulting benchtop stable compounds from 469 nm (blue)
to 540 nm (green). A further shift of the fluorescence maximum to 594 nm (red) can
be achieved by switching from 2-thienyl to p-aminophenyl groups. A comparison of the
optoelectronic properties of selected C-substituted DBA(Mes)2 derivatives with those
of the isostructural anthracene analogues unveiled the following: (i) The DBA core
is a much better electron acceptor. (ii) The emission colors of DBAs fall in the visible
range of the spectrum (blue to orange), while anthracenes emit exclusively in the
near-ultraviolet to blue wavelength regime. (iii) DBAs show significantly higher solid-state
quantum yields.