Synthesis, characterization, and photophysical properties of
covalent-linked ferrocene–porphyrin–single-walled carbon
nanotube triad hybrid
Haiying Zhao
b
, Yizhou Zhu
a
, Chen Chen
a
, Lin He
a
, Jianyu Zheng
a,
*
a
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
b
College of Chemistry and Chemical Engineering, Inner Mongolia University, Huhhot 010021, China
ARTICLE INFO
Article history:
Received 11 April 2012
Accepted 9 June 2012
Available online 23 June 2012
ABSTRACT
The ferrocene–porphyrin–single-walled carbon nanotube (Fc–H
2
P–SWCNT) triad hybrid
was prepared by amidation reaction between carboxylated SWCNT and aminoporphyrin
bearing an appended ferrocenyl substituent. The hybrid described here was fully character-
ized by a combination of analytical techniques such as Fourier transform infrared spectros-
copy, Raman, absorption and emission spectroscopy, atomic force and scanning electron
microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The steady
emission characteristics revealed the existence of the effective photoinduced electron
transfer among ferrocene, excited porphyrin moiety and SWCNT, which was further con-
firmed by the results of time-resolved transient absorption spectra. The final lifetime of
charge-separation state was observed to be 62.9 lsinN,N-dimethylformamide, which
was significant increased compared to the reference nanohybrid porphyrin–SWCNT and
the reported ferrocene–porphyrin–fullerene triad. Therefore, Fc–H
2
P–SWCNT triad hybrid
constructed by amidation is rationally expected to be an improved photon-to-electron con-
version system.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
Much attention has recently been paid on the studies of the
photoinduced electron transfer (PET) process in donor–
acceptor (D–A) systems to develop artificial photosynthetic
systems and molecular optoelectronic devices, in which por-
phyrin and fullerene (C
60
) are considered as attractive molec-
ular components due to their unique structures and rich
photoelectronic properties [1]. Compared with spherical
shape of C
60
, single-wall carbon nanotubes (SWCNTs) are
one-dimensional nanowires that are either metallic or semi-
conducting. They readily accept multi-charges [2], which
can then be transported under nearly ideal conditions along
the tubular SWCNT axis [3]. The electrical conductivity,
morphology, and good chemical stability of SWCNTs are
promising features that stimulate their integration into pho-
tovoltaic systems or electronic devices combining with photo-
excited electron donors, such as porphyrins [4–7]. In fact, a
number of porphyrin–SWCNT nanohybrids, constructed by
p–p and Van der Waals [8–15], polymer wrapping [16–18], elec-
trostatic interaction [19–24] or covalent bond [25–34],have
been built in the past decade, and efficient PET from the sin-
glet excited porphyrin to attached SWCNT has been achieved
resulting in the formation of charge separation state with
high quantum yields.
To functionalize without damaging the p-electronic struc-
ture of SWCNTs, noncovalent attachments of porphyrin to
SWCNTs seem to be promising over the covalent attachments
0008-6223/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2012.06.018
* Corresponding author: Fax: +86 22 2350 5572.
E-mail address: jyzheng@nankai.edu.cn (J. Zheng).
CARBON
50 (2012) 4894– 4902
Available at www.sciencedirect.com
journal homepage: www.elsevier.com/locate/carbon