Communication
RSC Advances
Acknowledgements
The work is supported by National Natural Science Foundation
of China (no. 21076147), Natural Science Foundation of Tianjin
(no. 10JCZDJC23700), National International S&T Cooperation
Foundation of China (nO. 2012DFG41980) and Independent
Innovation Foundation of Tianjin University (2013).
Notes and references
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Fig. 5 The HOMO, LUMO, HOMO–LUMO gap and energy level of
corrole–fullerene dyad 3a.
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the closely attached fullerene moiety in 3a. Hence, a proposed
photo-induced electron transfer should occur between corrole
and fullerene as described in other corrole–fullerene
conjugates.17
In order to further understand the electronic and geomet-
rical structures of the corrole–fullerene dyad, ab initio quantum
mechanical calculations were performed with TD-DFT variant
hybrid density functional theory (B3LYP) in conjunction with
the 6-31G (d) basis set as implemented in the Gaussian 09
program package.36 The distances of “center to center ” and
“edge to edge”, calculated from the geometrical structure of 3a,
˚
˚
are 15.8 A and 10.2 A, respectively (see the energy-optimized
structure of 3a shown in Fig. S11†). In addition, Fig. 5 shows the
frontier highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) generated from theoret-
ical calculation. The result is similar to those reported previ-
ously.17,27 The HOMO (ꢁ4.75 eV) locates on the corrole moiety,
while the LUMO (ꢁ3.07 eV) resides totally on the fullerene cage
of 3a. Furthermore, part of the HOMO is also observed on the
meso-phenylene spacer of the dyad, suggesting considerable
interaction between the donor and acceptor units. Thus, the
calculated distribution of MO manifested the proposed intra-
13 I. Aviv and Z. Gross, Chem. Commun., 2007, 1987–1999.
14 S.-L. Lai, L. Wang, C. Yang, M.-Y. Chan, X. Guan, C.-C. Kwok
and C.-M. Che, Adv. Funct. Mater., 2014, 24, 4655–4665.
15 I. McConnell, G. H. Li and G. W. Brudvig, Chem. Biol., 2010,
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molecular electron transfer from the excited corrole to the
cꢁ
fullerene in gaining of charge-separated state corrolec+–C60
.
16 D. M. Guldi, Chem. Soc. Rev., 2002, 31, 22–36.
17 F. D'Souza, R. Chitta, K. Ohkubo, M. Tasior, N. K. Subbaiyan,
M. E. Zandler, M. K. Rogacki, D. T. Gryko and S. Fukuzumi,
J. Am. Chem. Soc., 2008, 130, 14263–14272.
Conclusions
In conclusion, we reported the synthesis and characterization of
novel corrole–fullerene dyad 3a–c. By tracing the fragments in 18 M. Tasior, D. T. Gryko, M. Cembor, J. S. Jaworski, B. Ventura
mass spectrum, the possible decomposition route was deduced. and L. Flamigni, New J. Chem., 2007, 31, 247–259.
Next, the preliminary photo physical properties of the corrole– 19 T. Ding, E. A. Aleman, D. A. Modarelli and C. J. Ziegler,
fullerene dyad have been studied. Strong uorescence J. Phys. Chem. A, 2005, 109, 7411–7417.
quenching and uorescence lifetime reducing of corrole core in 20 D. T. Gryko, J. Piechowska, J. S. Jaworski, M. Galezowski,
3a indicated that electron transfer could take place between
excited corrole and fullerene. TD-DFT calculation was also
M. Tasior, M. Cembor and H. Butenschon, New J. Chem.,
2007, 31, 1613–1619.
employed to analyze the electronic and geometry structures. 21 L. Echegoyen and L. E. Echegoyen, Acc. Chem. Res., 1998, 31,
The desired distribution of MO theoretically conrmed that the 593–601.
dyad 3a has a strong propensity for intramolecular electron 22 S. Fukuzumi, I. Nakanishi, T. Suenobu and K. M. Kadish,
transfer from corrole to fullerene cage.
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RSC Adv., 2014, 4, 40758–40762 | 40761