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ChemComm
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DOI: 10.1039/C7CC09264D
COMMUNICATION
Journal Name
The absorption and emission spectra of selected
benzo[c]phenanthrenes are shown in Figure 2. The optical
propierties of this novel heterocycle are not significantly
modified by the effect of substituents. Chloro-substitued
derivative 3c shows a very similar behaviour to the parent
Notes and references
1
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compound 3a
, whereas in the presence of an alkynyl
2
a) P. Zhao, D. O. Nettleton, R. G. Karki, F. J. Zécri, S.-Y. Liu,
ChemMedChem, 2017, 12, 358. b) H. Lee, M. Fischer, B. K.
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substituent (3h) the emission maxima is slightly red-shifted
and a small increase of the fluorescence quantum yield is
observed (3a
,
Φ
f = 0.03; 3c
,
Φ
f = 0.01; 3h, Φf = 0.10) .
3a
3c
3h
1,0
0,8
0,6
0,4
0,2
0,0
3a
3c
3h
1,0
0,8
0,6
0,4
0,2
0,0
3
4
5
H. Helten, Chem. Eur. J., 2016, 22, 12972.
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260
280
300
320
340
360
(nm)
380
400
420
440
340 360 380 400 420 440 460 480 500 520 540
(nm)
λ
λ
,
1139. Selected examples: OLEDs: a) W. Zhang, F. Zhang, R.
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Figure 2. UV/vis absortion (left) and emission (right) spectra of selected BN-
benzo[c]phenanthrenes in cyclohexane.
In conclusion, the synthesis of a new family of BN-PAHs has
been reported. We have achieved the first synthesis of parent
BN-benzo[c]phenanthrene 3a, which shows helical chirality
and structural properties clearly different from that of the all-
carbon analogue. The synthesis was carried out under mild
conditions and in only three steps from commercially available
materials to give a remarkable 55% overall yield. Moreover,
this synthetic route has been applied to the highly efficient
preparation of Cl-substituted BN-PAHs, which served as
starting materials for the synthesis of diversely substituted BN-
benzo[c]phenanthrenes through post-functionalization by
cross-coupling reactions. Couplings of Cl-substituted BN-PAHs
had not been previously reported and were not
6
7
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straightforward, but
a careful optimization allowed the
development of reaction conditions that were compatible with
the azaborine system and good yields could be obtained in
Suzuki, Buchwald–Hartwig and Sonogashira coupling reactions.
It is worth noting that the compatibility of BN-aromatic
compounds with the conditions required for the coupling of
Csp2-Cl bonds opens the door to synthetic strategies based on
sequential functionalization of C–Br and C–Cl bonds, such as
the one reported in this work and many others that can be
envisioned for the preparation of BN-PAHs and their post-
functionalization.
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8
9
For functionalization of BN-naphthalene cores involving C-H
activation see: a) G. H. M. Davies, M. Jouffroy, F. Sherafat, B.
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Molander, J. Org. Chem., 2014, 79, 365.
We gratefully acknowledge Ministerio de Economía
y
11 CCDC 1581758 contains the supplementary crystallographic
data for this paper. These data are provided free of charge
by the Cambridge Crystallographic Data Centre.
12 E. R. Abbey, L. N. Zakharov, S.-Y. Liu, J. Am. Chem. Soc., 2008,
130, 7250.
13 A related observation has been reported previously for a
higher BN-helicene.: J. Am. Chem. Soc., 2012, 134, 19600.
14 M. K. Lakshman, P. L. Kole, S. Chaturvedi, J. H. Saugier, H. J.
C. Yeh, J. P. Glusker, H. L. Carrell, A. K. Katz, C. E. Afshar, W.-
M. Dashwood, G. Kenniston, W. M. Baird, J. Am. Chem. Soc.,
2000, 122, 12629.
Competitividad (MINECO, project CTQ2014-52488-R), Instituto
de Salud Carlos III (FEDER funds, ISCIII RETIC REDINREN
RD16/0009/0015), and University of Alcalá (projects
CCG2015/EXP-011, CCG2016/EXP-028, CCG2016/EXP-040) for
financial support. P. G. G. also thanks MINECO for a ‘‘Ramón y
Cajal’’ contract. A. A. thanks the University of Alcalá for a
predoctoral grant.
15 A. Abengózar, P. García-García, D. Sucunza, L. M. Frutos, O.
Castaño, D. Sampedro, A. Pérez-Redondo, J. J. Vaquero, Org.
Lett., 2017, 19, 3458.
Conflicts of interest
There are no conflicts to declare.
4 | J. Name., 2012, 00, 1-3
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