jp054601u_si_001.pdf (193.62 kB)
Spectroscopic and Excited-State Properties of Tri-9-anthrylborane III: Crystal and Spectroscopic Polymorphisms
journal contribution
posted on 2005-12-01, 00:00 authored by Eri Sakuda, Kiyoshi Tsuge, Yoichi Sasaki, Noboru KitamuraWe found that tri-9-anthrylborane (TAB) recrystallized from benzene produced both red cubic-like (R-form)
and orange hexagon-like crystals (O-form). In both crystal forms, six TAB molecules are arranged in a
honeycomb structure in the ab plane and benzene molecules are incorporated in the honeycomb structure,
whose spatial geometry and the total number of benzene rings in the unit cell are different between the two
forms: polymorphs with a different benzene content. In the R-form crystal, furthermore, interlayer stacking
between left- and right-handed helical TAB molecules was observed in the ac plane, while each layer composed
of stacked TAB molecules along the c axis was separated by benzene molecules in the O-form crystal, giving
rise to more dense packing of TAB in the R-form crystal as compared to that in the O-form. Reflecting the
crystal structures of the two forms, the charge transfer (CT) absorption and fluorescence spectra of the R-form
crystal were shifted to the longer wavelength as compared to those in the O-form (i.e., crystal and spectroscopic
polymorphisms) and, therefore, electronic interactions between TAB were stronger in the R-form as compared
to those in the O-form. Furthermore, in addition to the main absorption (λmaxa = 499 nm) and fluorescence
peaks (λmaxf = 570 nm), distinct absorption (λa = ∼470 nm) and fluorescence bands (λf = ∼600 nm) were
observed for the R-form crystal, while the relevant absorption band in the O-form crystal (λa = ∼460 nm)
or in solution (λa = ∼435 nm) was ambiguous. The results were discussed in terms of participation of the
higher energy second CT transition in TAB.