Star-shaped and linear nanosised molecules functionalized with hexa-peri-hexabenzocoronene: Synthesis and optical properties

Article abstract of DOI:10.1021/jo0480139

(Chemical Equation Presented) A synthetic strategy promising the establishment of a new star-shaped and linear polycyclic aromatic hydrocarbons (PAHs) family with distinct molecular topologies has been developed. The Sonogashira reaction between the iodid

Full text of DOI:10.1021/jo0480139

Star-Shaped and Linear Nanosized Molecules Functionalized with
Hexa-peri-hexabenzocoronene: Synthesis and Optical Properties
Xiao-Yu Cao, Hong Zi, Wei Zhang, Hua Lu, and Jian Pei*
The Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College
of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
jianpei@pku.edu.cn
Received November 9, 2004
A synthetic strategy promising the establishment of a new star-shaped and linear polycyclic aromatic
hydrocarbons (PAHs) family with distinct molecular topologies has been developed. The Sonogashira
reaction between the iodide derivatives 2a-e and phenylacetylene catalyzed with Pd(0) affords
3a-e in high yields. The Diels-Alder and decarbonylation reactions between 3a-e and tetraphe-
nylcyclophentadiene following the oxidation by FeCl3 produce the star-shaped and linear PAHs
5a-e containing a five-membered ring. The structural analysis and the optical properties of all
new compounds are performed by a combination of MALDI-TOF mass spectrometry, UV-vis, and
fluorescence spectrometry. The electronic and photophysical properties are studied by orthogonal
comparisons of the absorption and fluorescence spectra in THF solutions, which not only give insight
into the interactions among aromatic submoieties in each molecule and the effects of meta-
conjugation and para-conjugation on electronic delocalization, but also indicate effective conjugation
length variations from oligophenylacetylenes 3a-e to oligophenylene dendrimers 4a-e and PAHs
5a-e. The star-shaped 5c exhibits the highest aggregation in excited states compared with the
other four hexa-peri-hexabenzocoronene (HBC) derivatives.
CHART 1
Introduction
The well-defined geometric structures and fascinating
electronic properties of polycyclic aromatic hydrocarbons
(PAHs) have promoted their extensive use in liquid
crystalline materials, electronics and optoelectronics,
fullerenes and carbon nanotubes, and supramolecular
architectures, as well as theoretically interesting mol-
ecules.1 Such molecularly defined graphite model com-
pounds enrich the chemistry of polycyclic aromatic
hydrocarbons.2 “Fully benzenoid” hexa-peri-hexabenzo-
coronene (HBC) (as shown in Chart 1) and its larger
homologues developed by Mu¨llen represent an intriguing
PAH family.3 HBCs exhibit liquid crystalline properties
and hole transport capabilities and also emit light over
a broad range of wavelengths, paving the way for organic
photonic and electronic devices such as organic light-
emitting diodes(OLEDs), field effect transistors (FETs),
and solar cells.4
Recently, the breakthrough made by Mu¨llen has
provided an elegant approach to PAHs with diverse size
and shape in a straightforward manner.5 Since both
* To whom correspondence should be addressed. Fax: 86-10-
62758145.
10.1021/jo0480139 CCC: $30.25 © 2005 American Chemical Society
Published on Web 03/26/2005
J. Org. Chem. 2005, 70, 3645-3653
3645

Cao et al.
molecular size and boundary shape of PAHs influence
the electronic structures, energetics, and reactivities, it
is necessary to design and synthesize novel PAHs for the
thorough investigation of their structure-property rela-
tionships and the tuning of molecular properties toward
specific applications.6 Substituted monomeric HBCs self-
assemble in a face-to-face manner to form columnar
stacks with requisite nanophase separation of the side
chains.
tronic properties are investigated by orthogonal compari-
sons of the absorption and fluorescence spectra in dilute
solutions, which not only give insight into the interactions
among aromatic submoieties in each molecule, as well
as the effects of meta-conjugation and para-conjugation
on electronic delocalization, but also shed light on distinct
effective conjugation length variations from 3a-e to
4a-e as well as 5a-e.
Results and Discussion
During the past decades, truxene has been recognized
as a starting material for the construction of large
polyarenes and bowl-shaped fragments of the fullerenes,
liquid crystals, and C3 tripod materials in asymmetric
catalysis and chiral recognition.7 We prepared a series
of star-shaped oligothiophene-functionalized truxene de-
rivatives and novel π-conjugated dendrimers based on
truxene, which exhibited unique NMR behaviors, optical
properties, and electroluminescence.8 Moreover, among
organic π-conjugated materials with large energy band
gaps including poly-p-phenylene (PPP)9 and ladder-poly-
p-phenylene (LPPP),10 polyfluorene (PF)11 and oligofluo-
rene12 derivatives have been considered as the most
promising blue-light emitters due to their high photolu-
minescence (PL) efficiency, good charge transport ability,
thermal stability, and facile tunability of physical proper-
ties through chemical modification. Herein, we describe
a strategy to selectively functionalize one, two, or three
sides of both truxene and fluorene moieties. The elec-
Synthesis. Scheme 1 illustrates that the selective
iodination of each branch of truxene and fluorene rings
from readily available hexahexyl-substituted truxene
derivative 1 afforded their corresponding iodides 2a-e
according to a procedure to that found in the literature.13
We usually employed the iodide derivatives since they
readily undergo the Sonogashira reaction. We obtained
the iodides 2a-e in good yields by controlling the amount
of H5IO6 and I2.
(7) (a) Go´mez-Lor, B.; de Frutos, OÄ .; Echavarren, A. M. Chem.
Commun. 1999, 2431-2432. (b) Mehta, G.; Rao, H. S. P. Tetrahedron
1998, 54, 13325-13370. (c) Ansems, R. B. M.; Scott, L. T. J. Am. Chem.
Soc. 2000, 122, 2719-2724. (d) Rabideau, P. W.; Abdourazak, A. H.;
Marcinow, Z.; Sygula, R.; Sygula, A. J. Am. Chem. Soc. 1995, 117,
6410-6411. (e) Sygula, A.; Rabideau, P. W. J. Am. Chem. Soc. 2000,
122, 6323-6324. (f) Boorum, M. M.; Vasil’ev, Y. V.; Drewello, T.; Scott,
L. T. Science 2001, 294, 828-831. (g) Scott, L. T.; Boorum, M. M.;
McMahon, B. J.; Hagen, S.; Mack, J.; Blank, J.; Wegner, H.; de Meijere,
A. Science 2002, 295, 1500-1503. (h) Cherioux, F.; Guyard, L. Adv.
Funct. Mater. 2001, 11, 305-309. (i) Dijkstra, H. P.; Kruithof, C. A.;
Ronde, N.; van de Coevering, R.; Ramo´n, D. J.; Vogt, D.; van Klink, G.
P. M.; van Koten, G. J. Org. Chem. 2003, 68, 675-685. (j) Lambert,
C.; No¨ll, G.; Scha¨mlzlin, E.; Meerholz, K.; Bra¨uchle, C. Chem. Eur. J.
1998, 4, 2129-2135. (k) Perova, T. S.; Vij, J. K. Adv. Mater. 1995, 7,
919-922. (l) Fontes, E.; Heiney, P. A.; Ohba, M.; Haseltine, J. N.;
Smith, A. B. Phys. Rev. A. 1988, 37, 1329-1334. (m) Go´mez-Lor, B.;
de Frutos, OÄ .; Ceballos, P. A.; Granier, T.; Echavarren, A. M. Eur. J.
Org. Chem. 2001, 2001, 2107-2114. (n) de Frutos, OÄ .; Granier, T.;
Go´mez-Lor, B.; Jime´nez-Barbero, J.; Monge, M. AÄ .; Gutie´rrez-Puebla,
E.; Echavarren, A. M. Chem. Eur. J. 2002, 8, 2879-2890. (o) Ruiz,
M.; Go´mez-Lor, Santos, A.; Echavarren, A. M. Eur. J. Org. Chem. 2004,
2004, 858-866. (p) Kanibolotsky, A. L.; Berridge, R.; Skabara, P. J.;
Perepichka, I. F.; Bradley, D. D. C.; Koeberg, M. J. Am. Chem. Soc.
2004, 126, 13695-13702.
(8) (a) Pei, J.; Wang, J.-L.; Cao, X.-Y.; Zhou, X.-H.; Zhang, W.-B. J.
Am. Chem. Soc. 2003, 125, 9944-9945. (b) Cao, X.-Y.; Zhang, W.-B.;
Wang, J.-L.; Zhou, X.-H.; Lu, H.,; Pei, J. J. Am. Chem. Soc. 2003, 125,
12430-12431. (c) Cao, X.-Y.; Liu, X.-H.; Zhou, X.-H.; Zhang, Y.; Jiang,
Y.; Cao, Y.; Cui, Y.-X.; Pei, J. J. Org. Chem. 2004, 69, 6050-6058.
(9) (a) Grem, G.; Leditzky, G.; Ullrich, B.; Leising, G. Adv. Mater.
1992, 4, 36-37. (b) Yang, Y.; Pei, Q.; Heeger, A. J. J. Appl. Phys. 1996,
79, 934-939. (c) Marsitzky, D.; Mu¨llen, K. In Advances in Synthetic
Metals - Twenty Years of Progress in Science and Technology; Bernier,
P., Lefrant, S., Bidan, G., Eds.; Elsevier: Amsterdam, 1999; pp 1-97.
(10) (a) Scherf, U.; Mu¨llen, K. Macromol. Chem., Rapid Commun.
1991, 12, 489-497. (b) Scherf, U. J. Mater. Chem. 1999, 9, 1853-1864.
(11) (a) Pei, Q.; Yang, Y. J. Am. Chem. Soc. 1996, 118, 7416-7417.
(b) Setayesh S.; Grimsdale, A. C.; Weil, T.; Enkelmann, V.; Mu¨llen,
K.; Meghdadi, F.; List, E. J. W.; Leising G. J. Am. Chem. Soc. 2001,
123, 946-953. (c) Marsitzky, D.; Vestberg, R.; Blainey, P.; Tang, B.
T.; Hawker, C. J.; Carter, K. R. J. Am. Chem. Soc. 2001, 123, 6965-
6972. (d) Mu¨ller, D. C.; Falcou, A.; Reckefuss, N.; Rojahn, M.;
Wlederhirm, V.; Rudati, P.; Frohne, H.; Nuyken, O.; Becker, H.;
Meerholz, K. Nature 2003, 421, 829-833.
(1) (a) Clar, E. Polycyclic Hydrocarbons; Academic Press: New York,
1964. (b) Harvey, R. G. Polycyclic Aromatic Hydrocarbons; Wiley-
VCH: New York, 1997. (c) Hopf, H. Classics in Hydrocarbon Chemistry;
Wiley-VCH: Weinheim, Germany, 2000. (d) Carbon Rich Complex I/II.
Top. Curr. Chem. 1998, 196. (e) Diederich, F.; Rubin, Y. Angew. Chem.,
Int. Ed. Engl. 1992, 31, 1101-1123. (f) Boese, R.; Matzger, A. J.;
Mohler, D. L.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1995,
34, 1478-1481. (g) Tong, L.; Lau, H.; Ho, D. M.; Pascal, R. A., Jr. J.
Am. Chem. Soc. 1998, 120, 6000-6006. (h) Yamaguchi, S.; Swager, T.
M. J. Am. Chem. Soc. 2001, 123, 12087-12088. (i) Percec, V.; Glodde,
M.; Bera, T. K.; Miura, Y.; Shiyanovskaya, I.; Singer, K. D.; Balagu-
rusamy, V. S. K.; Heiney, P. A.; Schnell, I.; Rapp, A.; Spiess, H.-W.;
Hudson, S. D.; Duan, H. Nature 2002, 417, 384-387. (j) Sakurai, H.;
Daiko, T.; Hirao, T. Science 2003, 301, 1878. (k) Ajami, D.; Oeckler,
O.; Simon, A.; Herges, R. Nature 2003, 426, 819-821.
(2) (a) Clar, E. The Aromatic Sexter; Wiley: London, 1972. (b)
Zander, M. Polycyclische Aromaten; Teubner: Stuttgart, 1995. (c)
Goddard, R.; Haenel, M. W.; Herndon, W. C.; Kru¨ger, C.; Zander, M.
J. Am. Chem. Soc. 1995, 117, 30-41.
(3) (a) Berresheim, A. J.; Mu¨ller, M.; Mu¨llen, K. Chem. Rev. 1999,
99, 9, 1747-1786. (b) Watson, M. D.; Fethtenko¨tter, A.; Mu¨llen, K.
Chem. Rev. 2001, 101, 1267-1300. (c) Simpson, C. D.; Wu, J.; Watson,
M.; Mu¨llen, K. J. Mater. Chem. 2004, 14, 494-504. (d) Schmidt-Mende,
L.; Fechtenkotter, A.; Mu¨llen, K.; Moons, E.; Friend, R. H.; Mackenzie,
J. D. Science 2001, 293, 1119-1122. (e) Hill, J. P.; Jin, W. S.; Kosaka,
A.; Fukushima, T.; Ichihara, H.; Shimomura, T.; Ito, K.; Hashizume,
T.; Ishii, N.; Aida, T. Science 2004, 304, 1481-1483.
(4) (a) Christ, T.; Glu¨sen, B.; Greiner, A. J.; Kettner, A.; Sander,
R.; Stu¨mpflen, V.; Tsukruk, V.; Wendorff, J. H. Adv. Mater. 1997, 9,
48-52. (b) Tang, C. W.; VanSlyke, S. A. Appl. Phys. Lett. 1987, 51,
913-915. (c) van de Crass, A.; Stutzmann, M. N.; Bunk, O.; Nielsen,
M. M.; Watson, M. D.; Mu¨llen, K.; Chanzy, H. D.; Sirringhaus, H.;
Friend, R. H. Adv. Mater. 2003, 15, 495-499. (d) Kraft, A. ChemPhys-
Chem 2001, 2, 163-165. (e) Katz, H. E.; Lovinger, A. J.; Johnson, J.;
Kloc, C.; Siegrist, T.; Li, W.; Lin, Y.-Y.; Dodabalapur, A. Nature 2000,
404, 478-481. (f) Tang, C. W. Appl. Phys. Lett. 1986, 48, 183-185.
(5) (a) Stein, S. E.; Brown, R. L. J. Am. Chem. Soc. 1987, 109, 3721-
3729. (b) Mu¨ller, M.; Ku¨bel, C.; Mu¨llen, K. Chem. Eur. J. 1998, 4,
2099-2109. (c) Do¨tz, F.; Brand, J. D.; Ito, S.; Gherghel, L.; Mu¨llen, K.
J. Am. Chem. Soc. 2000, 122, 7707-7717. (d) Wu, J.; Watson, M. D.;
Tchebotareva, N.; Wang, Z.; Mu¨llen, K. J. Org. Chem. 2004, 69, 8194-
8204.
(12) (a) Wong, K.-T.; Chien, Y.-Y.; Chen, R.-T.; Wang, C.-F.; Lin,
Y.-T.; Chiang, H.-H.; Hsieh, P.-Y.; Wu, C.-C.; Chou, C.-H.; Su, Y.-O.;
Lee, G.-H.; Peng, S.-M. J. Am. Chem. Soc. 2002, 124, 11576-11577.
(b) Katsis, D.; Geng, Y. H.; Ou, J.-J.; Culligan, S. W.; Trajkovska, A.;
Chen, S. H.; Rothberg, L. J. Chem. Mater. 2002, 14, 1332-1339. (c)
Geng, Y. H.; Katsis, D.; Culligan, S. W.; Ou, J.-J.; Chen, S. H.;
Rothberg, L. J. Chem. Mater. 2002, 14, 463-470. (d) Wu, C.-C.; Liu,
T.-L.; Hung, W.-Y.; Lin, Y.-T.; Wong, K.-T.; Chen, R.-T.; Chen, Y.-M.;
Chien, Y.-Y. J. Am. Chem. Soc. 2003, 125, 3710-3711. (e) Geng, Y.
H.; Culligan, S. W.; Trajkovska, A.; Wallace, J. U.; Chen, S. H. Chem.
Mater. 2003, 15, 542-549. (f) Wu, F.-I.; Reddy, D. S.; Shu, C.-F.; Liu,
M. S.; Jen, A. K.-Y. Chem. Mater. 2003, 15, 269-274.
(6) The nonalternant PAHs were only developed recently by Mu¨llen.
(a) Wang, Z.; Tomovic´, Zˇ.; Kastler, M.; Pretsch, R.; Negri, F.; Enkel-
mann, V.; Mu¨llen, K. J. Am. Chem. Soc. 2004, 126, 7794-7795. (b)
Wu, J.; 1. (a) Tomovic´, Zˇ.; Enkelmann, V.; Mu¨llen, K. J. Org. Chem.
2004, 69, 5179-5186.
(13) Lee, S. H.; Nakamura, T.; Tsutsui, T. Org. Lett. 2001, 3, 2005-
2007.
3646 J. Org. Chem., Vol. 70, No. 9, 2005

Nanosized Molecules Functionalized with Hexa-peri-hexabenzocoronene
SCHEME 1a
SCHEME 2a
a Reagents and conditions: (i) H5IO6 (1/3 equiv), I2 (1/3 equiv),
CH3COOH/H2SO4/H2O (100:20:3), 60 °C; (ii) H5IO6 (2/3 equiv), I2
(2/3 equiv), CH3COOH/H2SO4/H2O (100:20:3), 60 °C; (iii) H5IO6
(1 equiv), I2 (1 equiv), CH3COOH/H2SO4/H2O (100:20:3), 60 °C.
The subsequent Sonogashira reaction between 2a and
phenylacetylene afforded 3a with one phenylacetylene
arm at the truxene moiety as shown in Scheme 2. We
also got 3b with two phenylacetylene arms and star-
shaped 3c with three phenylacetylene arms at the
truxene moiety. The linear compounds 3d and 3e with
one or two phenylacetylene arms at the fluorene moiety
were also obtained according to the same procedure in
good yields. The Diels-Alder reactions of 3a-c with
excess commercially available tetraphenylcyclopentadi-
enone following the decarbonylation generated the de-
sired oligophenylene dendrimers 4a-c, respectively
(Scheme 3).2b The same procedure also produced the
linear oligophenylene compounds 4d and 4e. Although
crude products in this reaction exhibited very deep color,
the pure white solids 4a-e were obtained after repeated
washing with hot methanol.
a Reagents and conditions: (i) phenylacetylene, Pd(PPh3)4, CuI,
NEt3, toluene.
did not affect the properties of desired materials (see the
Supporting Information).14
The structure of all intermediate compounds has been
1
confirmed by H and 13C NMR, MALDI-TOF MS char-
The final oxidative cyclodehydrogenation of dendrimers
4a-e with FeCl3 in CH2Cl2 furnished target PAHs 5a-e
in quantitative yields (Scheme 4). Due to the existence
of five-membered rings which makes a significant dif-
ference between our molecules and the Mu¨llen-type
PAHs, a small amount of FeCl3 did not oxidize the 3D
skeleton to form the PAH plane. We found that longer
reaction time and greater amounts of FeCl3 (more than
20 equiv per C-C bond) were keys to promote the
conversions in this step, especially for 5b and 5c.
Unfortunately, the excess FeCl3 sometimes produced
some chlorinated byproducts although such byproducts
acterizations, as well as elemental analysis after purified
by standard column chromatography. The target PAHs
derivatives 5a-e were characterized by MALDI-TOF MS
spectroscopy. From MALDI-TOF MS spectra, we ob-
served the exact loss of 12 hydrogen atoms for 5a and
5d, 24 for 5b and 5e, and 36 for 5c, respectively.
UV-vis and Photoluminescence Properties in
Solution. The UV-vis absorption and fluorescence
spectra of the novel intermediate and target compounds
(14) Iyer, V. S.; Wehmeier, M.; Brand, J. D.; Keegstra, M. A.; Mu¨llen,
K. Angew. Chem., Int. Ed. Engl. 1997, 36, 1604-1610.
J. Org. Chem, Vol. 70, No. 9, 2005 3647

Cao et al.
SCHEME 3a
with the absorption spectra of 3a-e, with the increase
of phenylacetylene substituents, we observed that the
absorption λmax increased accordingly for both truxene
and fluorene derivatives. It would be interesting to
investigate the spectra of truxene derivatives (3-5c) and
fluorene derivatives (3-5e), which represented meta-
conjugation and para-conjugation on electronic delocal-
ization, respectively. Although 3c contained three func-
tionalized phenylacetylene groups, its absorption λmax was
slightly blue-shifted in comparison with that of 3e (two
phenylacetylene groups). Similar results were observed
from the absorption spectra between 4c and 4e. However,
the spectrum of 5e was very similar to that of 5c except
for some small shoulders, which were due to the domi-
nating HBC skeletons. These results indicated that the
para-conjugation in the structure was more helpful for
the extension of effective conjugation length than star-
shaped meta-conjugation. The UV-vis absorption spectra
of 5a, 5b, and 5d peaked at 367, 370, and 363 nm,
respectively. Those of 5c and 5e were less structured,
with a red shift to 373 nm, and became broad. The
absorption spectra of 5a-e exhibited the characteristic
profile of HBCs, which were almost the same as the
Mu¨llen-type HBC derivatives. It is clear that the aro-
matic chromophores are mainly HBC moieties and their
intramolecular π-electronic conjugation is not effective.
This observation is distinct from the current size-absorp-
tion λmax relationship for all-benzenoid analogues.
From the emission spectra, we observed that the
maximum peak of 5e (373 nm) slightly red-shifted in
comparison with that of 5d (363 nm). For the series of
truxene HBC derivatives, the peak at about 490 nm
obviously amplified with the increase of HBC segments
in their emission spectra while decreased at about 370
nm. 5c gave a broad less-structured emission with the
maximum peak at about 491 nm in comparison with the
other four compounds and n-alkyl-substituted HBCs,
which indicated that a higher degree of aggregation
existed in 5c than those of others; 5c exhibited unique
optical properties in comparison with Mu¨llen-type HBCs.
The investigation of the optical properties of all com-
pounds also demonstrated that a novel series of HBCs
derivatives with fused five-membered rings were suc-
cessfully prepared.
Conclusion
In conclusion, the initial utilization of truxene and
fluorene moieties as basic building blocks to construct a
novel large PAH family containing HBC chromophores
has been presented. The thorough investigation of the
photophysical properties of acetylenes 3, oligophenylene
dendrimers 4, and PAHs 5 in THF solutions indicates
unique π-electron delocalization among intramolecular
chromophores for our compounds. The star-shaped trux-
ene-cored HBC 5c exhibits the highest degree of aggrega-
tion in solution in comparison with the other four HBCs,
and such aggregation is enhanced with the increase of
the HBC moiety. The difference between the effects of
meta-conjugation and para-conjugation on electronic
delocalization are demonstrated. We have opened versa-
tile opportunities to create novel large PAHs with com-
pletely distinct molecular topologies as well as unique
electronic and photoelectronic properties, suggesting the
a Reagents and conditions: (i) tetraphenylcyclopentadienone,
diphenyl ether, reflux.
were measured in THF. The solution concentration of all
compounds was about 1.0 × 10-6 M. Table 1 summarizes
the optical properties of all new compounds. Figure 1
presents the combined absorption and fluorescence spec-
tra of PAHs 5a-e in dilute THF solutions, while the
orthogonal comparisons of those of compounds 3-5 are
recorded in Figures 2 and 3. From Figures 2 and 3, we
observed that both absorption and fluorescence spectra
of the oligophenylene dendrimers 4a-e were slightly
blue-shifted in comparison with the corresponding oli-
gophenyl acetylenes 3a-e as shown in Figure 4, while
significant red-shift was observed when these precursors
were planarized to PAHs 5a-e in accordance with the
change of effective conjugation length. In comparison
3648 J. Org. Chem., Vol. 70, No. 9, 2005

Nanosized Molecules Functionalized with Hexa-peri-hexabenzocoronene
SCHEME 4a
a Reagents and conditions: (i) FeCl3 (3 eq/H), CH2Cl2/CH3NO2.
or 400 MHz spectrometer using CDCl3 or CD2Cl2 as solvent
potential utility of these materials in electronic and
optoelectronic devices.
in all cases. In the NMR assignments, Fr and Tr present
fluorene and truxene groups, respectively. UV-vis spectra
were recorded on a UV-vis spectrometer. PL spectra were
carried out on a luminescence spectrometer. MALDI-TOF mass
spectra were recorded on a time-of-flight (TOF) mass spec-
trometer using a 337 nm nitrogen laser with CCA as matrix.
Experimental Section
General Methods. All commercial chemicals were used as
received. 1H and13C NMR spectra were recorded on a 200, 300,
J. Org. Chem, Vol. 70, No. 9, 2005 3649

Cao et al.
TABLE 1. Photophysical Properties of Compounds 3a-5e in THF Solutions
molecules
molecular weight (g/mol)
absorbance λmax (nm)
emission λmax (nm)
ꢀa (105 L/mol‚cm)
3a
3b
3c
3d
3e
4a
4b
4c
4d
4e
5a
5b
5c
5d
5e
947.5
1047.6
1147.7
434.6
349, 331, 310, 295
332, 350
334, 351
338, 323
349
309, 296
318, 311
322
348, 365
1.1
357, 374
2.0
362, 381
330, 344
1.6
0.44
1.1
534.8
359, 378, (403)
343, 359
1304.0
1760.5
2217.1
791.1
1.4
347, 363
1.2
351, 367
1.6
314
324
336, 339
0.29
0.65
0.86
1.7
1247.7
1291.9
1736.4
2180.8
779.0
345
415, 397, 367, 351
419, 400, 370
373
412, 394, 363, 346
437, 373
459, 469, 479, 490, 513, 526
460, 480, 490, 512, 524
461, (470), 491, 512
460, 474, 490, 515, 525
464, 496
1.4
1.0
1223.5
1.4
a The solution concentration of all compounds was about 1.0 × 10-6 M.
FIGURE 1. Absorption (left) and photoluminescence spectra (right) of PAHs in THF solutions at room temperature.
FIGURE 2. Absorption (left) and photoluminescence spectra (right) of 3a-e in THF solutions at room temperature.
2d and 2e were synthesized according to a procedure similar
to that found in the literature.13
Hz), 8.08-8.11 (1H, d, J ) 8.7 Hz), 7.76-7.77 (1H, d, J ) 1.5
Hz), 7.69-7.72 (1H, dd, J ) 8.7 Hz, J ) 1.5 Hz), 7.38-7.47
(6H, m), 2.90-2.99 (6H, m), 2.01-2.08 (6H, m), 0.85-0.90
(36H, m), 0.46-0.63 (30H, m). 13C NMR (CDCl3, 75 MHz, ppm,
δ): 153.6, 153.6, 153.4, 145.5, 144.9, 144.8, 144.1, 140.3, 140.1,
140.1, 140.0, 138.6, 138.3, 137.3, 135.0, 131.4, 126.5, 126.3,
126.07, 126.0, 125.9, 124.7, 124.6, 124.6, 124.5, 122.2, 122.1,
55.9, 55.7, 55.6, 55.6, 37.0, 36.9, 36.9, 36.7, 31.5, 31.4, 31.4,
29.5, 29.4, 29.4, 23.9, 23.8, 22.2, 13.8.
2b. A mixture of compound 1 (5.00 g, 5.91 mmol) and 10
mL of solvent mixture (CH3COOH/H2SO4/H2O ) 100:20:3) was
heated to 60 °C with vigorous stirring, followed by adding
H5IO6 (0.46 g, 1.96 mmol) and I2 (1.00 g, 3.94 mmol). The
mixture was stirred at 80 °C under nitrogen atmosphere. After
the elementary iodine almost disappeared (for 2b, it took about
2 d), the mixture was cooled to room temperature and 150 mL
2a. A mixture of compound 1 (5.00 g, 5.91 mmol) and 10
mL of solvent mixture (CH3COOH/H2SO4/H2O ) 100:20:3) was
heated to 60 °C with vigorous stirring, followed by adding
H5IO6 (0.23 g, 0.98 mmol) and I2 (0.50 g, 1.97 mmol). The
mixture was stirred at 80 °C under nitrogen atmosphere. After
the elementary iodine almost disappeared (for 2a, it took about
2 d), the mixture was cooled to room temperature and 150 mL
water was added. The whole mixture was extracted with ether,
and the organic phase was washed with water, 2 M aqueous
Na2CO3, 5% Na2S2O3 aqueous solution, and saturated NaCl
solution and dried over MgSO4. After removal of the solvent,
the product was purified by recrystallization twice from
ethanol to afford 2a (4.77 g, 83%) as a colorless crystal. 1H
NMR (CDCl3, 300 MHz, ppm, δ): 8.35-8.37 (2H, d, J ) 6.6
3650 J. Org. Chem., Vol. 70, No. 9, 2005

Nanosized Molecules Functionalized with Hexa-peri-hexabenzocoronene
FIGURE 3. Absorption (left) and photoluminescence spectra (right) of 4a-e in THF solutions at room temperature.
using petroleum as eluent to afford a colorless solid (3.33 g,
85%). 1H NMR (CDCl3, 500 MHz, ppm, δ): 8.34-8.37 (3H, m),
7.62-7.63 (1H, d, J ) 1.5 Hz), 7.60-7.62 (2H, dd, J ) 8.0 Hz,
J ) 1.5 Hz), 7.57-7.59 (1H, dd, J ) 8.0 Hz, J ) 1.5 Hz), 7.45-
7.47 (2H, m), 7.35-7.41(7H, m), 2.86-3.01 (6H, m), 2.07-2.13
(6H, m), 0.85-0.90 (36H, m), 0.58-0.62 (18H, m), 0.45-0.55
(12H, m). 13C NMR (CDCl3, 125 MHz, ppm, δ): 153.7, 153.6,
153.5, 145.4, 145.0, 140.7, 140.1, 140.1, 138.5, 138.4, 137.7,
131.6, 129.7, 128.3, 128.1, 126.4, 126.0, 125.2, 124.6, 124.6,
124.4, 123.5, 122.1, 120.6, 90.3, 89.5, 55.6, 55.6, 37.0, 36.9, 36.8,
31.4, 29.4, 23.8, 22.2, 13.8. MS (MALDI-TOF): calcd for C71H94
m/z 946.74 (100.0), 947.74 (80.4), 948.74 (30.7), 949.75 (8.3),
950.75 (1.6), 948.75 (1.1), found 946.61 (100.0), 947.62 (85.5),
948.62 (31.8), 949.63 (9.3). Anal. Calcd for C71H94: C, 90.00;
H, 10.00. Found: C, 89.78; H, 10.15.
3b. The procedure is analogous to that described for 3a
1
(yield: 81%). H NMR (CDCl3, 500 MHz, ppm, δ): 8.33-8.37
(3H, m), 7.63 (2H, s), 7.60-7.62 (4H, dd, J ) 8.0 Hz, J ) 1.5
Hz), 7.58-7.59 (2H, d, J ) 8.5 Hz), 7.46-7.48 (1H, m), 7.36-
7.41 (8H, m), 2.90-3.02 (6H, m), 2.07-2.12 (6H, m), 0.82-
0.95 (36H, m), 0.59-0.63 (18H, m), 0.45-0.51 (12H, m). 13C
NMR (CDCl3, 125 MHz, ppm, δ): 153.6, 153.5, 145.6, 145.3,
140.5, 140.4, 139.9, 138.6, 137.9, 137.7, 131.6, 129.8, 128.3,
128.2, 126.6, 126.1, 125.2, 124.6, 124.5, 123.4, 122.2, 120.8,
90.2, 89.6, 55.7, 37.0, 36.8, 31.4, 31.4, 29.4, 23.9, 22.2, 22.2,
13.8. MS (MALDI-TOF): calcd for C79H98 m/z 1046.77 (100.0),
1047.77 (89.3), 1048.77 (38.1), 1049.78 (11.5), 1050.78 (2.5),
1048.78 (1.3), found 1047.10 (100.0), 1048.10 (85.8), 1049.10
(37.2), 1050.10 (11.4). Anal. Calcd for C79H98: C, 90.57; H, 9.43.
Found: C, 90.18; H, 9.75.
3c. The procedure is analogous to that of 3a (yield: 87%).
1H NMR (CDCl3, 200 MHz, ppm, δ): 8.33-8.37 (3H, d, J )
8.4 Hz), 7.58-7.64 (12H, m), 7.37-7.44 (9H, m), 2.87-3.01
(6H, m), 2.04-2.18 (6H, m), 0.87-0.99 (36H, m), 0.58-0.65
(18H, t, J ) 6.5 Hz), 0.47-0.51 (12H, m). 13C NMR (CDCl3, 50
MHz, ppm, δ): 155.0, 153.6, 145.8, 140.2, 137.9, 131.6, 129.9,
128.3, 128.2, 125.2, 124.5, 123.3, 121.0, 116.0, 90.1, 89.8, 55.8,
36.9, 31.4, 29.4, 23.9, 22.2, 13.8. MS (MALDI-TOF): calcd for
C87H102 m/z 1146.80 (100.0), 1147.80 (98.3), 1148.80 (46.3),
1149.81 (15.3), 1150.81 (3.6), 1148.81 (1.5), found 1146.52
(100.0), 1147.51 (92.9), 1148.44 (49.0), 1149.49 (19.3), 1150.48
(9.5). Anal. Calcd for C87H102: C, 91.04; H, 8.96. Found: C,
90.85; H, 9.05.
FIGURE 4. Comparion of the absorption spectra of 3c-5c
in THF solutions at room temperature.
water was added. The whole mixture was extracted with ether,
and the organic phase was washed with water, 2 M aqueous
Na2CO3, 5% Na2S2O3 aqueous solution, and saturated NaCl
solution and dried over MgSO4. After removal of the solvent,
the product was purified by recrystallization several times
from ethanol to afford crude 2b (4.54 g, 70%) as a colorless
solid, which contained a slight amount of 2a, and used directly.
2c. A mixture of compound 1 (5.00 g, 5.91 mmol) and 15
mL of solvent mixture (CH3COOH/H2SO4/H2O ) 100:40:3) was
heated to 60 °C with vigorous stirring, followed by addition of
3 mL of CHCl3, H5IO6 (1.15 g, 4.9 mmol), and I2 (2.50 g, 9.85
mmol). The mixture was stirred at 80 °C under nitrogen
atmosphere. A small amount of H5IO6 was added to the
1
mixture until H NMR indicated that the reaction was com-
pletd (for 2c, it took about 5 d), the mixture was cooled to room
temperature, and 150 mL of water was added. The brown
precipitate was filtered and purified by recrystallization three
times from ethanol to afford 2c (6.51 g, 90%) as a white solid.
1H NMR (CDCl3, 300 MHz, ppm, δ): 7.92-8.14 (3H, d, J ) 12
Hz), 7.72-7.80 (3H, s), 7.64-7.72 (3H, d, J ) 12 Hz), 2.72-
2.98 (6H, m), 1.88-2.16 (6H, m), 0.76-1.08 (36H, m), 0.59-
0.76 (18H, t, J ) 9.0 Hz), 0.29-0.58 (12H, m). 13C NMR (CDCl3,
100 MHz, ppm, δ): 155.9, 145.0, 139.5, 137.6, 135.3, 131.5,
126.2, 92.6, 55.9, 36.7, 31.4, 29.3, 23.8, 22.2, 13.8.
3a. A flame-dried flask with a magnetic stirrer was loaded
with 2a (4.00 g, 4.12 mmol), Pd(PPh3)4 (95.2 mg, 0.0824 mmol),
and CuI (31.7 mg, 0.1648 mmol). Under nitrogen atmosphere,
dry toluene (150 mL) and triethylamine (30 mL) were added,
and the mixture was stirred for 20 min, yielding a yellow
transparent solution. Phenylacetylene (0.91 mL, 8.24 mmol)
was then added via a syringe, and the flask was closed. The
reaction mixture, which turned to yellow-orange suspension
over 30 min, was stirred vigorously for 2 d. The suspension
was filtered, and the filtrate was concentrated under vacuum.
The residue was purified by flash column chromatography
3d. The procedure is analogous to that of 3a (yield: 84%).
1H NMR (CDCl3, 500 MHz, ppm, δ): 7.68-7.70 (1H, dd, J )
8.0 Hz, J ) 1.5 Hz), 7.66-7.68 (1H, d, J ) 7.5 Hz), 7.56-7.58
(2H, dd, J ) 8.0 Hz, J ) 1.5 Hz), 7.51-7.53 (1H, dd, J ) 7.5
Hz, J ) 1.5 Hz), 7.50 (1H, d, J ) 1.5 Hz), 7.31-7.38 (6H, m),
1.95-1.98 (4H, t, J ) 8.5 Hz), 1.09-1.13 (4H, q, J ) 7.0 Hz),
1.00-1.08 (8H, m), 0.75-0.78 (6H, t, J ) 7.5 Hz), 0.57-0.65
(4H, m). 13C NMR (CDCl3, 125 MHz, ppm, δ): 151.0, 150.7,
141.4, 140.4, 131.5, 130.6, 128.3, 128.1, 127.4, 126.8, 125.9,
123.4, 122.8, 121.3, 119.9, 119.5, 90.5, 89.2, 55.1, 40.3, 31.5,
29.7, 23.7, 22.5, 13.9. MS (MALDI-TOF): calcd for C33H38 m/z
J. Org. Chem, Vol. 70, No. 9, 2005 3651

Cao et al.
434.30 (100.0), 435.30 (37.3), 436.30 (6.5), found 434.24 (100.0),
435.21 (55.1), 436.21 (8.9). Anal. Calcd for C33H38: C, 91.19;
H, 8.81. Found: C, 90.89; H, 8.91.
(68.8), 1676.99 (34.4), 1677.99 (12.2), 1678.99 (3.2), 1675.99
(1.9); found 1674.83 (100.0), 1673.85 (71.8), 1675.88 (70.1),
1676.87 (35.8), 1677.85 (14.6), 1678.83 (7.3). Anal. Calcd for
C135H138: C, 92.10; H, 7.90. Found: C, 92.43; H, 7.85.
3e. The procedure is analogous to that of 3a (yield: 80%).
1H NMR (CDCl3, 500 MHz, ppm, δ): 7.66-7.68 (2H, d, J )
8.0 Hz), 7.56-7.58 (4H, dd, J ) 8.0 Hz, J ) 1.5 Hz), 7.52-
7.54 (2H, dd, J ) 7.5 Hz, J ) 1.0 Hz), 7.50-7.51 (2H, d, J )
1.0 Hz), 7.34-7.39 (6H, m), 1.97-2.00 (4H, m), 1.09-1.14 (4H,
q, J ) 7.0 Hz), 1.01-1.07 (8H, m), 0.76-0.78 (6H, t, J ) 7.5
Hz), 0.58-0.64 (4H, m). 13C NMR (CDCl3, 125 MHz, ppm, δ):
151.0, 140.6, 131.6, 130.7, 128.3, 128.2, 125.9, 123.3, 121.9,
119.9, 90.3, 89.7, 55.2, 40.4, 31.5, 29.7, 23.7, 22.6, 13.9. MS
(MALDI-TOF): calcd for C41H42 m/z 534.33 (100.0), 535.33
(46.2), 536.34 (10.4), 537.34 (1.5); found 534.12 (100.0), 535.07
(70.1), 536.07 (21.0), 537.06 (3.9). Anal. Calcd for C41H42: C,
92.08; H, 7.92. Found: C, 92.21; H, 7.57.
4c. Compound 3c (1.00 g, 0.872 mmol), tetraphenyl cyclo-
pentadienone (1.51 g, 3.92 mmol), and 15 mL of diphenyl ether
were deoxygenated and then heated to reflux under nitrogen
atmosphere overnight. After the mixture was cooled to room
temperature, the diphenyl ether was removed under reduced
pressure and the residue was purified by column chromatog-
raphy (silica gel, PE/CH2Cl2 ) 2:1) to remove some of the rest
tetraphenyl cyclopentadienone, which was further purified by
recrystallization from methanol six to eight times to give a
1
light pale powder (1.74 g, 90%). H NMR (CDCl3, 500 MHz,
ppm, δ): 7.62-7.63 (3H, d, J ) 8.0 Hz), 6.90-6.92 (3H, d, J )
8.0 Hz), 6.80-6.85 (63H, m), 6.70-6.72 (15H, m), 2.42-2.48
(6H, m), 1.41-1.47 (6H, m), 0.97-1.01 (12H, q, J ) 7.0 Hz),
0.75-0.76 (24H, m), 0.69-0.72 (18H, t, J ) 7.5 Hz), -0.02 to
-0.01 (12H, m). 13C NMR (CDCl3, 125 MHz, ppm, δ): 151.8,
144.1, 140.7, 140.6, 140.4, 140.3, 140.1, 138.4, 137.6, 137.4,
131.5, 131.4, 131.4, 129.1, 126.5, 126.5, 126.3, 125.3, 125.2,
125.1, 122.8, 54.9, 36.7, 31.7, 29.5, 23.4, 22.5, 14.0. MS
4a. Compound 3a (1.00 g, 1.06 mmol), tetraphenyl cyclo-
pentadienone (0.61 g, 1.59 mmol), and 10 mL of diphenyl ether
were deoxygenated and then heated to reflux under nitrogen
atmosphere overnight. After being cooled to room temperature,
the diphenyl ether was removed under reduced pressure and
the residue was purified by column chromatography (silica gel,
PE/CH2Cl2 ) 5:1) to afford a yellow solid, which was further
purified by recrystallization from methanol to give a white
powder (1.32 g, 96%). 1H NMR (CDCl3, 500 MHz, ppm, δ):
8.30-8.32 (1H, d, J ) 8.0 Hz), 8.25-8.26 (1H, m), 7.77-7.78
(1H, d, J ) 8.0 Hz), 7.29-7.41 (6H, m), 6.96-6.97 (2H, m),
6.74-6.87 (25H, m), 2.88-2.94 (2H, m), 2.68-2.76 (4H, m),
1.98-2.04 (2H, m), 1.90-1.95 (2H, m), 1.62-1.67 (2H, m),
0.81-0.97 (36H, m), 0.17-0.72 (30H, m). 13C NMR (CDCl3, 125
MHz, ppm, δ): 153.6, 153.5, 151.9, 145.0, 144.4, 144.2, 140.7,
140.6, 140.4, 140.3, 140.2, 138.8, 138.2, 138.0, 137.3, 131.6,
131.4, 126.5, 126.3, 126.1, 125.8, 125.4, 125.2, 125.1, 124.6,
124.5, 122.9, 122.0, 122.0, 55.3, 55.2, 36.5, 36.8, 31.7, 31.5, 31.4,
29.6, 29.4, 29.4, 23.7, 23.5, 22.3, 22.3, 13.9, 13.8. MS (MALDI-
TOF) (CCA + AgTFA): calcd for C99H114+ m/z 1303.90 (100.0),
1302.89 (92.3), 1304.90 (53.7), 1305.90 (18.3), 1306.91 (5.0),
1307.91 (1.0), found 1304.30 (100.0), 1303.31 (97.8), 1305.36
(64.5); calcd for [M + Ag]+ C99H114Ag+ m/z 1411.80 (100.0),
1410.80 (73.1), 1412.80 (67.9), 1409.80 (65.4), 1413.80 (36.5),
1412.81 (14.8), 1414.81 (14.5), 1413.81 (5.2), 1415.81 (3.7),
1411.81 (1.2), found 1412.34 (100.0), 1410.34 (80.9), 1413.30
(79.0), 1411.31 (74.1), 1414.47 (41.4), 1415.37 (27.8); calcd for
(MALDI-TOF) (CCA + AgTFA): calcd for [M + Ag]+ C171H162
-
Ag+ m/z 2325.18 (100.0), 2323.18 (66.1), 2324.18 (63.2), 2326.18
(58.8), 2327.18 (35.9), 2322.17 (34.3), 2324.17 (31.9), 2328.19
(19.7), 2326.19 (19.0), 2327.19 (8.6), 2329.19 (6.6), 2330.19
(1.9), 2325.19 (1.5), found 2325.25 (100.0), 2324.26 (95.8),
2326.25 (90.3), 2323.27 (73.6), 2327.24 (59.0), 2322.28 (54.9),
2328.32 (39.6); calcd for [M - C6H13]+ [C165H149 + m/z 2131.17
]
(100.0), 2132.17 (90.1), 2133.18 (56.5), 2130.17 (53.8), 2134.18
(25.8), 2135.18 (8.8), 2136.19 (2.8), 2132.18 (2.2), found 2131.35
(100.0), 2132.30 (88.9), 2133.33 (55.6), 2130.32 (56.2), 2134.28
(27.7), 2135.31 (12.6). Anal. Calcd for C171H162: C, 92.64; H,
7.36. Found: C, 92.28; H, 7.05.
4d. Compound 3d (1.50 g, 3.45 mmol), tetraphenyl cyclo-
pentadienone (1.99 g, 5.18 mmol), and 20 mL of diphenyl ether
were deoxygenated and then heated to reflux under nitrogen
atmosphere overnight. After the mixture was cooled to room
temperature, the diphenyl ether was removed under reduced
pressure and the residue was purified by column chromatog-
raphy (silica gel, PE/CH2Cl2 ) 5:1) to afford a light yellow solid
which was further purified by recrystallization from methanol
to give a white powder (2.57 g, 94%). 1H NMR (CDCl3, 500
MHz, ppm, δ): 7.46-7.47 (1H, m), 7.17-7.21 (3H, m), 6.89-
6.91 (1H, d, J ) 8.0 Hz), 6.83-6.87 (21H, m), 6.78-6.81 (1H,
dd, J ) 8.0 Hz, J ) 1.5 Hz), 6.75-6.77 (5H, m), 1.71-1.77
(2H, m), 1.57-1.63 (2H, m), 1.11-1.17 (4H, q, J ) 7.0 Hz),
0.92-1.04 (8H, m), 0.79-0.82 (6H, t, J ) 7.0 Hz), 0.19-0.29
(4H, m). 13C NMR (CDCl3, 125 MHz, ppm, δ): 150.6, 149.0,
141.1, 140.7, 140.6, 140.3, 140.3, 139.6, 138.1, 131.4, 131.3,
129.9, 126.5, 126.4, 126.2, 126.0, 125.2, 125.1, 122.4, 119.3,
118.0, 54.5, 40.6, 31.5, 29.8, 23.2, 22.7, 14.0. MS (MALDI-TOF)
(CCA + AgTFA): calcd for C61H58 m/z 790.45 (100.0), 791.46
(68.7), 792.46 (23.2), 793.46 (5.0), found 790.44 (100.0), 791.45
(74.9), 792.46 (30.5); calcd for [M + Ag]+ C61H58Ag+ m/z 897.36
(100.0), 899.36 (92.9), 898.36 (67.8), 900.36 (63.8), 899.37
(23.2), 901.37 (22.4), 900.37 (5.2), 902.37 (4.8), found 899.34
(100.0), 897.33 (85.0), 900.31 (58.4), 898.31 (58.1), 901.29
(18.2), 902.37 (5.9). Anal. Calcd for C61H58: C, 92.61; H, 7.39.
Found: C, 92.23; H, 7.48.
4e. Compound 3e (1.00 g, 1.87 mmol), tetraphenyl cyclo-
pentadienone (2.16 g, 5.61 mmol), and 25 mL of diphenyl ether
were deoxygenated and then heated to reflux under nitrogen
atmosphere overnight. After the mixture was cooled to room
temperature, the diphenyl ether was removed under reduced
pressure and the residue was purified by column chromatog-
raphy (silica gel, PE/CH2Cl2 ) 4:1) to afford a yellow solid,
which was further purified by recrystallization from methanol
to give a white powder (2.14 g, 93%). 1H NMR (CDCl3, 300
MHz, ppm, δ): 6.95-6.98 (2H, d, J ) 7.5 Hz), 6.74-6.82 (52H,
m), 6.67-6.70 (2H, d, J ) 7.5 Hz), 1.36-1.50 (4H, m), 1.21-
1.26 (4H, q, J ) 6.9 Hz), 0.95-1.06 (8H, m), 0.96-0.91 (6H, t,
[M - C6H13]+ C93H101 m/z 1218.79 (100.0), 1217.79 (96.7),
+
1219.80 (52.7), 1220.80 (18.0), 1221.80 (4.3), 1218.80 (1.5),
found 1219.31 (100.0), 1218.29 (96.0), 1220.32 (51.0), 1221.34
(17.1), 1222.36 (6.8). Anal. Calcd for C99H114: C, 91.19; H, 8.81.
Found: C, 91.08; H, 8.47.
4b. Compound 3b (1.00 g, 0.955 mmol), tetraphenyl cyclo-
pentadienone (1.10 g, 2.87 mmol), and 12 mL of diphenyl ether
were deoxygenated and then heated to reflux under nitrogen
atmosphere overnight. After being cooled to room temperature,
the diphenyl ether was removed under reduced pressure and
the residue was purified by column chromatography (silica gel,
PE/CH2Cl2 ) 4:1) to afford a yellow solid, which was further
purified by recrystallization from methanol to give a white
powder (1.65 g, 98%). 1H NMR (CDCl3, 200 MHz, ppm, δ):
8.19-8.21 (m, 1H), 7.70-7.74 (2H, m), 7.25-7.32 (2H, m),
6.72-6.96 (55H, m), 2.60-2.70 (4H, m), 2.45-2.55 (2H, m),
1.83-1.85 (2H, m), 1.42-1.60 (4H, m), 0.85-0.98 (12H, m),
0.59-0.78 (48H, m), 0.08-0.42 (18H, m). 13C NMR (CDCl3, 50
MHz, ppm, δ): 153.4, 151.8, 144.6, 143.8, 140.6, 140.6, 140.4,
140.3, 140.2, 138.6, 137.9, 137.7, 137.3, 131.5, 131.4, 129.2,
126.5, 126.3, 125.2, 125.1, 55.0, 36.8, 31.6, 31.5, 29.6, 29.4, 23.7,
23.5, 22.4, 22.3, 14.0, 13.9. MS (MALDI-TOF) (CCA + AgT-
FA): calcd for [M + Ag]+ C135H138Ag+ m/z 1866.99 (100.0),
1868.99 (92.9), 1867.99 (75.5), 1869.99 (70.2), 1865.98 (65.7),
1867.98 (61.0), 1869.00 (37.8), 1870.99 (33.7), 1870.00 (14.1),
1872.00 (13.1), 1871.00 (5.6), 1873.00 (3.9), 1872.01 (1.0), found
1867.83 (100.0), 1868.79 (99.6), 1866.79 (79.8), 1869.75 (66.4),
1865.75 (57.1), 1870.79 (39.9), 1871.76 (22.7); calcd for [M -
C6H13]+ C129H125 m/z 1674.98 (100.0), 1675.98 (70.3), 1673.98
3652 J. Org. Chem., Vol. 70, No. 9, 2005

Nanosized Molecules Functionalized with Hexa-peri-hexabenzocoronene
J ) 7.2 Hz), -0.22- -0.08 (4H, m). 13C NMR (CDCl3, 50 MHz,
ppm, δ): 148.9, 140.6, 140.6, 140.3, 140.1, 139.0, 138.2, 131.4,
131.3, 129.8, 126.5, 126.4, 125.7, 125.2, 125.0, 117.9, 54.2, 41.0,
31.7, 30.2, 23.2, 22.8, 14.1. MS (MALDI-TOF) (CCA + AgT-
FA): calcd for C97H82 m/z 1247.65 (100.0), 1246.64 (91.6),
1248.65 (54.0), 1249.65 (19.2), 1250.66 (5.1), 1251.66 (1.1),
found 1248.11 (100.0), 1247.14 (95.2), 1249.14 (51.6), 1250.11
(22.0), 1251.63 (6.0); calcd for [M + Ag]+ C97H82Ag+ m/z 1355.55
(100.0), 1354.55 (72.5), 1356.55 (67.4), 1353.55 (66.4), 1357.55
(35.6), 1356.56 (14.0), 1358.56 (13.7), 1357.56 (4.5), 1359.56
(3.4), found 1356.11 (100.0), 1357.06 (74.9), 1355.10 (74.3),
1354.09 (64.4), 1358.07 (39.1), 1359.08 (14.6), 13560.03 (7.8).
Anal. Calcd for C97H92: C, 93.38; H, 6.62. Found: C, 93.07; H,
6.83.
5a. To a flame-dried flask with a magnetic stirrer was added
a solution of compound 4a (100 mg, 0.0767 mmol) in 250 mL
of dry dichloromethane. The solution was degassed by bubbling
nitrogen for 20 min, and then iron(III) trichloride (1.50 g, 9.20
mmol) dissolved in 15 mL of nitromethane was added dropwise
via a syringe. A constant nitrogen stream was carried out
during the entire reaction, and the reaction was quenched by
adding 300 mL of methanol after 0.5 h. The yellow precipitate
was collected and washed repetitively with methanol until the
filtrate was colorless. The light yellow powder was dried under
vacuum to give 5a in quantitative yield (99 mg, 100%). MS
(MALDI-TOF) (CCA + AgTFA): calcd for C99H102 m/z 1291.80
(100.0), 1290.80 (89.6), 1292.80 (53.8), 1293.81 (20.2), 1294.81
(5.5), 1292.81 (1.5), 1295.81 (1.1), found 1293.46 (100.0),
1294.45 (96.3), 1291.42 (95.9), 1290.43 (82.9), 1292.41 (78.0),
1289.39 (65.4), 1295.44 (58.1), 1297.36 (36.2), 1298.41 (28.5),
1299.34 (27.2); calcd for [M + Ag]+ C99H102Ag+ m/z 1400.71
(100.0), 1398.71 (89.1), 1397.70 (79.8), 1399.70 (74.1), 1399.71
(49.2), 1401.71 (45.7), 1402.71 (16.0), 1401.72 (4.9), 1403.72
(4.7), 1402.72 (1.7), found 1400.39 (100.0), 1401.42 (88.9),
1398.40 (77.8), 1399.42 (76.3), 1402.45 (68.9), 1403.41 (50.4),
1397.37 (45.9), 1396.34 (45.9), 1404.44 (37.8); calcd for [M -
C6H13]+ [C93H89]+ m/z 1206.70 (100.0), 1205.70 (95.4), 1207.70
(50.5), 1208.71 (17.7), 1209.71 (4.5), 1207.71 (1.3), found
1206.24 (100.0), 1207.26 (95.8), 1208.27 (73.3), 1209.23 (45.3),
1205.23 (28.8).
5c. To a flame-dried flask with a magnetic stirrer was added
a solution of compound 4c (100 mg, 0.0451 mmol) in 300 mL
of dry dichloromethane. The solution was degassed by bubbling
nitrogen for 20 min, and then iron(III) trichloride (2.65 g, 16.3
mmol) dissolved in 27 mL of nitromethane was added dropwise
via a syringe. A constant nitrogen stream was carried out
during the entire reaction, and the reaction was quenched by
adding 400 mL of methanol after 4 h. The yellow brown
precipitate was collected and washed repetitively with metha-
nol until the filtrate was colorless. The yellow powder was
dried under vacuum to give 5c in quantitative yield (98 mg,
100%). MS (MALDI-TOF) (CCA + AgTFA): calcd for [M -
C6H13]+ [C165H113 + m/z 2094.89 (100.0), found 2097.19 (100.0);
]
calcd for [M - C6H13 + Cl]+ m/z 2128.85 (100.0), found 2133.17
(100.0); calcd for [M - C6H13 + 3Cl]+ m/z 2198.79 (100.0), found
2201.13 (100.0); calcd for [M - C6H13 + 4Cl]+ m/z 2233.76
(100.0), found 2235.07 (100.0); calcd for [M - C6H13 + 5Cl]+
m/z 2168.73 (100.0), found 2270.00 (100.0).
5d. To a flame-dried flask with a magnetic stirrer was added
a solution of compound 4d (100 mg, 0.127 mmol) in 250 mL of
dry dichloromethane. The solution was degassed by bubbling
nitrogen for 20 min, and then iron(III) trichloride (2.47 g, 15.2
mmol) dissolved in 25 mL of nitromethane was added dropwise
via a syringe. A constant nitrogen stream was carried out
during the entire reaction, and the reaction was quenched by
adding 300 mL of methanol after 0.5 h. The yellow brown
precipitate was collected and washed repetitively with metha-
nol until the filtrate was colorless. The light yellow powder
was dried under vacuum to give 5d in quantitative yield (98
mg, 100%). MS (MALDI-TOF) (CCA): calcd for C61H46 m/z
778.36 (100.0), 779.36 (67.8), 780.37 (23.1), 781.37 (5.1), found
778.25 (100.0), 779.21 (72.5), 780.22 (25.9), 781.27 (8.2).
5e. To a flame-dried flask with a magnetic stirrer was added
a solution of compound 4e (100 mg, 0.0801 mmol) in 250 mL
of dry dichloromethane. The solution was degassed by bubbling
nitrogen for 20 min, and then iron(III) trichloride (3.12 g, 19.2
mmol) dissolved in 31 mL of nitromethane was added dropwise
via a syringe. A constant nitrogen stream was carried out
during the entire reaction, and the reaction was quenched by
adding 300 mL of methanol after 4 h. The yellow brown
precipitate was collected and washed repetitively with metha-
nol until the filtrate was colorless. The light yellow powder
was dried under vacuum to give 5e in quantitative yield (98
mg, 100%). MS (MALDI-TOF) (Di): calcd for C97H58 m/z
1223.46 (100.0), 1222.45 (91.9), 1224.46 (53.8), 1225.46 (18.7),
1226.47 (5.0), 1227.47 (1.1), found 1226.62 (100.0), 1227.65
(81.8), 1225.60 (63.1), 1224.58 (58.5), 1228.61 (45.9), 1229.63
(21.4), 1230.71 (16.4).
5b. To a flame-dried flask with a magnetic stirrer was added
a solution of compound 4b (100 mg, 0.0568 mmol) in 250 mL
of dry dichloromethane. The solution was degassed by bubbling
nitrogen for 20 min, and then iron(III) trichloride (2.21 g, 13.6
mmol) dissolved in 22 mL of nitromethane was added dropwise
via a syringe. A constant nitrogen stream was carried out
during the entire reaction, and the reaction was quenched by
adding 300 mL of methanol after 0.5 h. The yellow brown
precipitate was collected and washed repetitively with metha-
nol until the filtrate was colorless. The yellow powder was
dried under vacuum to give 5a in quantitative yield (99 mg,
100%). MS (MALDI-TOF) (CCA): calcd for C135H114 m/z
1735.90 (100.0), 1736.90 (75.4), 1734.89 (65.8), 1737.90 (37.6),
1738.91 (14.0), 1739.91 (4.1), 1740.91 (1.0), found 1734.75
(100.0), 1735.82 (99.9), 1736.75 (91.9), 1733.75 (82.8), 1737.75
(72.9), 1738.76 (62.2), 1739.69 (58.3); calcd for [M - C6H13]+
Acknowledgment. This research was financially
supported by the Major State Basic Research Develop-
ment Program (No. 2002CB613401) from the Mini-
stry of Science and Technology and by the National
Natural Science Foundation of China (NSFC. 90201021,
50473016, 20425207 and 50103001).
Supporting Information Available: Additional data.
This material is available free of charge via the Internet at
http://pubs.acs.org.
[C129H101]
+ m/z 1650.79 (100.0), 1651.80 (72.7), 1649.79 (69.7),
1652.80 (34.6), 1653.80 (11.7), 1654.81 (3.4), 1650.80 (1.1),
found 1650.69 (100.0), 1651.74 (86.6), 1649.72 (80.9), 1652.72
(53.2), 1653.69 (33.5), 1654.67 (22.4).
JO0480139
J. Org. Chem, Vol. 70, No. 9, 2005 3653