We successfully tune ultralong organic room-temperature
phosphorescence
(UORTP) by a simple strategy of precisely modifying nitrogen atoms
on Phosphorescence Units, and colorful ultralong
phosphorescence can be achieved. We for the first time investigate
the structure–function relationship between phosphorescence
properties and molecular structures of Phosphorescence Units. With BCz and BCz-1 as comparison, eight new Phosphorescence
Units were synthesized by introducing one or two nitrogen
atoms to the naphthalene moiety. For all the 10 Phosphorescence
Units, their room-temperature ultralong phosphorescence in
the PMMA film should be assigned to monomer phosphorescence from intrinsic
T1 decay. For Phosphorescence Units series
I (BCz, NBCz-1, NBCz-2, NBCz-3, NBCz-4, NBCz-5, and NBCz-6), introducing
one nitrogen atom to the naphthalene moiety can significantly affect
the phosphorescence properties of Phosphorescence Units, and the effect is quite complicated. For modification on the inner
ring, the T1 energy level of NBCz-1 decreases, and the
red shift of UORTP occurs while the T1 energy level of
NBCz-2 increases and the blue shift of UORTP happens. For modification
on the outer ring, no phosphorescence color change is observed for
NBCz-3 and NBCz-4, but their phosphorescence lifetimes vary notably
due to different intersystem crossing efficiencies; as the modification
site approaches the central five-member ring, the T1 energy
levels of NBCz-5 and NBCz-6 decrease, and their UORTP red shifts dramatically.
For Phosphorescence Units series II (BCz, 2NBCz,
BCz-1, and 2NBCz-1), introducing two nitrogen atoms to the outer six-member
ring reduces energy level of T1 excitons and leads to incredible
red shift of UORTP for BCz and 2NBCz while surprisingly energy levels
of T1 excitons rise and UORTP blue shifts for BCz-1 and
2NBCz-1. Under the condition of proper modification sites, it is true
that the more the additional nitrogen atoms, the more red-shifted
the ultralong phosphorescence. This study may expand our knowledge
of organic phosphorescence and lay the foundation for its future applications.