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minutes at room temperature, probably due to the small
activation Gibbs energy,
G‡298K, of the dissociation process
between ZnCP and T3 (n = 8) (
G‡298K between ZnCP’ and 1,4-
Conflicts of interest
There are no conflicts to declare.
DOI: 10.1039/C9CC02866H
∆
∆
di(pyridin-4-yl)benzene was found to be 61.7 kJ·mol-1, Figure
S11, ESI†). Consequently, it is assumed that the proximity of the
three ZnCPs to each other increased via the penetration
process. As expected, the Glaser reaction of ZnCP with T3 (n = 8)
selectively afforded the trimer, ZnCP3 (Figure 3c). ZnCP3 was
isolated in 10% yield, by silica gel filtration and GPC. Molecular
ion peaks of ZnCP3 were detected by high-resolution MALDI-
TOF MS spectrometry (m/z = 7844.83). In the 1H NMR spectrum
of ZnCP3, six different doublet peaks corresponding to the
Notes and references
1
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(a) K. M. Smith, K. M. Kadish, and R. Guilard, Eds, The
Porphyrin Handbook, Academic Press, San Diego, 2000, Vol. 1
β
protons of porphyrins, and one singlet peak corresponding to
alkyne protons were confirmed (Figure 5). The integral ratio of
all protons to alkyne protons was 12:1. Consequently, it was
−
20. (b) D. Dolphin, Eds, The Porphyrins, Academic Press,
New York, 1979
D. M. Guldi and N. Martín, Eds, Fullerenes : From Synthesis to
Optoelectronic Properties, Springer, Dordrecht, 2002
.
β
3
.
revealed that the numbers of coordination points in the
templates could control the axis lengths of the porphyrin-
containing hollow structures.
4
(a) T. Yamaguchi, N. Ishii, K. Tashiro and T. Aida, J. Am. Chem.
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The high coplanarity between porphyrins led to efficient
elongation of π−conjugation. UV-Vis absorption spectroscopy
revealed that the Q band of porphyrins in ZnCP2 exhibited one
major peak around 720 nm, while that in linear porphyrin dimer
ZnP2 was split into two peaks around 670 nm and 730 nm
(Figure 4a). Generally, the dihedral angle of two porphyrins
linked by a diyne varied with the rotation of the diyne.
Conversely, the dihedral angle of two porphyrins in ZnCP2 or
ZnCP3 were assumed to be almost 0° due to the hollow
structure, which resulted in one Q band,14 although two Q
bands assigned to rotation isomers were observed in the
5
6
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,
spectrum of ZnP2. π-conjugated hollow structure,
15 Due to the
2729.
(a) P. S. Bols and H. L. Anderson, Acc. Chem. Res. 2018, 51
,
ZnCP3 exhibited absorbance almost in the near-infrared region.
In conclusion, we developed a two-step template method for
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porphyrin-containing hollow structures with long effective π-
conjugations. During the oligomerization, the numbers of 1,4-
di(pyridin-4-yl)benzene units could control the axis lengths of
the porphyrin-containing hollow structures due to the high
affinity to square porphyrin dimers. The linker lengths of the
templates and the association constant between square
porphyrin dimers and templates affected the reaction rate. The
9
template method is expected to be applied to longer
conjugated porphyrin-containing hollow structures.
π-
Acknowledgements
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This research was supported by financial supports (JST CREST
Grant Number JPMJCR1331, Environment Research and
Technology Development Fund of the ERCA Japan Grant
Number 5RF-1802, JSPS KAKENHI Grant Numbers 18H05158
and 17K14446, Mitsubishi Foundation, Nagase Science and
Technology Foundation, Terumo Foundation for Life Science
and Arts, Yazaki Memorial Foundation for Science and
Technology, Asahi Glass Foundation, The Ogasawara
Foundation for Promotion of Science & Engineering, and The
Amada Foundation, Izumi Science and Technology Foundation).
We thank Dr. Shima (Shimadzu Corporation) for mass analysis
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2014, 43, 1374. (b) Y. Chiba, M. Liu, Y. Tachibana, T. Fujihara,
Y. Tsuji and J. Terao, Chem. Asian. J., 2017, 12, 1900.
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of ZnCP2 and ZnCP3
.
4 | J. Name., 2012, 00, 1-3
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