We present a spectroscopic investigation on the effect of changing the position where carbazole is attached to biphenyl in carbazolebiphenyl (CBP) on the triplet state energies and the propensity to excimer formation. For this, two CBP derivatives have been prepared with the carbazole moieties attached at the (
para
) 4- and 4
′
-positions (
p
CBP) and at the (
meta
) 3- and 3
′
-positions (
m
CBP) of the biphenyls. These compounds are compared to analogous
m
CDBP and
p
CDBP, i.e. two highly twisted carbazoledimethylbiphenyls, which have a high triplet energy at about 3.0 eV and tend to form triplet excimers in a neat film. This torsion in the structure is associated with localization of the excited state onto the carbazole moieties. We find that in
m
CBP and
p
CBP, excimer formation is prevented by localization of the triplet excited state onto the central moiety. As conjugation can continue from the central biphenyls into the nitrogen of the carbazole in the
para
-connected
p
CBP, emission involves mainly the benzidine. By contrast, the
meta
-linkage in
m
CBP limits conjugation to the central biphenyl. The associated shorter conjugation length is the reason for the higher triplet energy of 2.8 eV in
m
CBP compared with the 2.65 eV in
p
CBP.
Computational Protocol to Calculate the Phosphorescence Energy of Pt(II) Complexes: Is the Lowest Triplet Excited State Always Involved in Emission? A Comprehensive Benchmark Study
