Triflic Acid-Promoted Adamantylation and tert-Butylation of Pyrene: Fluorescent Properties of Pyrene-Decorated Adamantanes and a Channeled Crystal Structure of 1,3,5-Tris(pyren-2-yl)adamantane

Article abstract of DOI:10.1021/acs.joc.0c01060

Triflic acid-promoted 1-adamantylation and tert-butylation of pyrene at positions 2 and 2,7 along with the synthesis of compounds having one-, two-, and three-pyrenyl groups attached to the adamantane scaffold are disclosed. Fluorescent properties of these compounds and channeled crystal structure of the 1,3,5-tris(pyren-2-yl)adamantane containing chloroform as a guest are also presented.

Full text of DOI:10.1021/acs.joc.0c01060

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Article
Triflic acid-promoted adamantylation and tert-butylation of pyrene:
fluorescent properties of pyrene-decorated adamantanes and a
channeled crystal structure of 1,3,5-tris(pyren-2-yl)adamantane.
Anna Wrona-Piotrowicz, Anna Makal, and Janusz Zakrzewski
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01060 • Publication Date (Web): 07 Aug 2020
Downloaded from pubs.acs.org on August 7, 2020
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Triflic acid-promoted adamantylation and tert-butylation of pyrene:
fluorescent properties of pyrene-decorated adamantanes and a chan-
neled crystal structure of 1,3,5-tris(pyren-2-yl)adamantane.
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*,†
‡
†
Anna Wrona-Piotrowicz, Anna Makal and Janusz Zakrzewski
†
Department of Organic Chemistry, Faculty of Chemistry, University of Lodz, ꢀꢁꢂꢃꢁ ꢄꢅ, ꢆꢄ-ꢇꢈꢉ ꢊꢋꢌꢍ, Poland
Biological and Chemical Research Center, Faculty of Chemistry, ꢎꢏꢐꢑꢒꢓꢔꢐꢕꢖ ꢋꢗ ꢘꢁꢓꢔꢁꢙ, ꢚꢙꢐꢓꢃꢐ ꢐ ꢘꢐꢛꢜꢓꢖ 101,
‡
02-089 Warszawa, Poland
Supporting Information Placeholder
ABSTRACT: Triflic acid-promoted 1-adamantylation and tert-butylation of pyrene at positions 2 and 2, 7 along with the synthesis
of compounds having one-, two- and three pyrenyl groups attached to the adamantane scaffold is disclosed. Fluorescent properties
of these compounds and channeled crystal structure of the 1,3,5-tris(pyren-2-yl)adamantane containing chloroform as a guest are
also
presented.
INTRODUCTION
have been no reports on the extension of its scope to other
alkyl halides.
1
Pyrene 1 (Figure 1) is a fascinating fluorophore and one of
the most promising starting materials for preparing of a pleth-
2
ora of organic optoelectronic materials. Two alkyl-substituted
pyrene derivatives, 2-tert-butylpyrene 2 and 2,7-di-tert-
butylpyrene 3 have been widely used as useful starting materi-
als in numerous syntheses of dyes that feature special molecu-
3
lar shapes and suppressed aggregation properties. Moreover,
the latter compound proved to be an efficient acceptor for
4
triplet-triplet annihilation and a π-donor for semiconductive
5
charge transfer cocrystals. To date, both compounds could be
obtained via Friedel-Crafts alkylation of pyrene with tert-butyl
chloride in the presence of a Lewis acid (aluminum chloride or
bromide). This reaction is unusual because electrophiles usual-
Figure 1. Formulae of compounds 1-3.
2a
RESULTS AND DISCUSSION
ly attack pyrene at positions 1, 3, 6 or 8. Moreover, there
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In continuation of our earlier work on triflic acid (TfOH)-
promoted Friedel-Crafts pyrene chemistry, we became inter-
systems in the solid state (e.g. encapsulating crystals and were
6
9
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
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3
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3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
used in syntheses of porous aromatic frameworks (PAFs)).
ested in elaborating a synthetic route to pyrenes bearing other
bulky tertiary alkyl groups at C(2) and C(7) using this
superacid as a promoter. The adamantyl group seemed espe-
cially interesting because physicochemical properties of
adamantyl-substituted compounds may be different from those
The adamantane skeleton was also used as a rigid linker be-
1
0
tween chromophoric groups. Therefore, molecules bearing
several pyrenyl groups in a well-defined spatial arrangement
might be of interest for developing solid-state emitters, sen-
sors, or self-assembled nanomaterials.
7
of their tert-butyl-substituted counterparts. Moreover, in
In this study, we report the results of this research along with
the basic fluorescent properties of the synthesized pyrene
derivatives 4-7 (Table 1) and the crystal structure of
tripyrenyladamantane 7 encapsulating molecule of the solvent
contrast to the tert-butyl group, the rigid adamantane scaffold
offers a possibility of attachment, via the Friedel-Crafts chem-
istry, of two, three or four aryl group to the tertiary carbons. It
has been demonstrated that di-, tri- and tetraaryl adamantanes
have a great tendency to form various types of supramolecular
Table 1. Optimized conditions for the adamantylation of pyrene.
0
1
2
3
4
5
6
7
8
9
0
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2
3
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7
8
9
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2
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6
7
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9
0
(chloroform).
Entry
AdaX
Pyrene: AdaX: TfOH
mmole)
Reaction
time
Product
(Isolated yield, %)
4 (93)
a
(
1
2
1-AdaBr
1-AdaOH
1 : 1 : 4
1 : 1 : 4
5 min
5 min
30 min
30 min
1 h
4 (84)
3
1-AdaBr
1 :2.2 : 4
1 :2.2 : 4
1 : 2.2 : 4
1 : 2.2 : 4
1 : 2.2 : 4
3 : 1 : 12
3 : 1 : 12
4.5 : 1 : 18
5 (91)
4
1-AdaCl
5 (87)
5
1-AdaOH
5 (95)
6
2-AdaBr
30 min
1 h
5 (83)
7
2-AdaOH
5 (87)
8
1,3-AdaBr2
1,3-Ada(OH)2
1,3,5-Ada(OH)3
4 h
6 (62)
9
4 h
6 (49)
10
6 h
7 (63)
a
Reactions were carried out in dichloromethane (10 mL) at r.t.; Ada = adamantyl.
We found that pyrene 1 smoothly reacts with 1-adamantanol
or 1-bromoadamantane in the presence of excess of TfOH in
dichloromethane at room temperature to afford, depending on
the reaction conditions compound 4 or 5. To obtain pure 4, not
contaminated with 5, pyrene and adamantyl compound were
used at a molar ratio 1:1 and the reaction was stopped after 5
min (Entry 1, 2). On the other hand, at the pyrene to
adamantyl compound molar ratio of 1:2.2 and prolonged reac-
tion times (30min - 1h) diadamantylpyrene 5 was formed in
high yields (Entries 3-7). It is also worthy to note that com-
pound 4 can also be obtained in practically the same yield
using 2-bromoadamantane or 2-adamantanol as alkylating
agents (Table 1, Entries 6-7). This suggests the intermediacy
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of 2-adamantyl cation, which is known to rapidly isomerize to
its 1-isomer.
Figure 2. Electronic absorption (a) and emission (b) spectra of
compounds 2-7 in argon-saturated dichloromethane solutions.
Absorption spectra were run at c = 5 x 10 M. Emission spectra
were obtained with an excitation at 340 nm for solution having the
same absorbance (0.10) at this wavelength.
1
1, 12
1
2
3
4
5
6
7
8
9
-
6
Having in hands an efficient protocol for the synthesis of 4
and 5 we became interested in its application for the synthesis
of compounds having two and three pyrenyl units linked to the
adamantane skeleton. To our pleasure, we found that the reac-
tion of 3 equiv. of pyrene with 1,3-dibromoadamantane or
adamantane-1,3-diol in the presence of TfOH yielded, after 4
h, 1,3-bis(pyren-2-yl)adamantane 6 in 62% and 49% yield,
respectively (Entries 8, 9). Furthermore, the reaction of 4.5
equiv. of pyrene with adamantane-1,3,5-triol gave after 6 h,
All investigated compounds showed absorption and emission
bands assignable to the isolated, monomeric pyrene
fluorophore. There was no evidence for the formation of
intramolecular excimers by 6 and 7 (negligible emission at
~450 nm). This means that the rigid adamantane skeleton
efficiently keeps pyrenyl moieties electronically isolated from
each other. However, there was a significant difference in the
solid-state emission of compounds 3 and 5 (normalized emis-
sion spectra in the solid state in Supporting Information).
While the former compound showed the structured emission
characteristic of isolated pyrene fluorophore, the latter dis-
played excimer emission (λmax ~ 450 nm). Therefore the 1-
adamantyl group, unlike the tert-butyl group, does not protect
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
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0
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1
,3,5-tris(pyren-2-yl)adamantane (7) in 63% yield (Table 1,
Entry 10).
We also found out that our protocol can be used for alternative
synthesis of tert-butylpyrenes 2 and 3 (see the Supporting
Information for details). Both tert-butyl halides and tert-
butanol afford the expected products in high yields (86-96%).
In our opinion, this procedure is more convenient than the
procedures described in literature, which use aluminum hal-
ides as promoter.
2
,7-disubstituted pyrene against the aggregation.
Unexpectedly, we found that solution of 7 in CDCl in a NMR
3
tube slowly deposited crystals in a form of large, yellowish
elongated blocs. They tended to lose transparency and trans-
form into a powder within seconds after extracting from moth-
er solution. Nevertheless, we succeeded in X-ray diffraction
structure determination of a single crystal suspended in a drop
of the solvent. The molecular structure of 7 is shown in Figure
Formation of the 2- and 2,7- substituted products in the reac-
tion of pyrene with tert-butyl halides is usually explained as
due to bulkiness of the tert-butyl group (these positions are
2
a
relatively less sterically hindered) . In our opinion the same
explanation may be valid for reactions with adamantyl com-
pounds.
3
. The three pyrene units are differently inclined with respect
We studied electronic absorption and emission spectra of
compounds 2-7. The spectra obtained for diluted solutions in
dichloromethane are shown in Figure 2 (Table contains the
photophysical data in Supporting Information).
to the idealized plane containing the main adamantane axis
◦
and C10, H10 atoms. The inclination angles are 67.4(5) ,
◦
◦
15.6(6) and 21.9(5) for pyrene moieties I, II and III respec-
tively. They also show some deviation from planarity and are
to some extent bent roughly along the short pyrene axis. The
angles between the average planes of the terminal rings within
1.00
2
3
4
5
6
7
◦
◦
◦
a
A
the pyrene fragments are 4.2(3) , 2.9(3) and 6.9(3) for pyrene
I, II and III, respectively.
0.75
0.50
0.25
0.00
300
325
350
375
 [nm]
700
600
500
400
300
200
100
0
2
b
3
4
5
6
7
Figure 3. Molecular structure of 7. Atomic displacement parame-
ters represented at 50% probability level. C atoms numbered 11 –
26 constitute pyrene I, C atoms 31 – 46 constitute pyrene II and C
atoms 51 – 66 constitute pyrene III moieties.
The crystal contains infinite channels (~7.5% of the unit cell
volume) spreading in [100] direction filled with highly disor-
dered chloroform molecules (Figure 4).
350
375
400
425
450
475

[nm]
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release it when chloroform is absent in the surrounding medi-
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um. Such a behavior promises possible applications of 7 and
its derivatives as crystal containers for various substances. In
addition, it is worthy to note that all of the synthesized
pyrenyladamantanes are expected to be easily functionalized
by electrophilic substitution, making possible a tuning of their
photophysical and supramolecular properties.
In conclusion, we have elaborated simple and efficient syn-
thetic route for introduction of tert-butyl and 1-adamantyl
groups into positions 2- and 2,7- of pyrene. It allowed synthe-
sis of compounds having two-and three pyrenyl groups at-
tached to the adamantane scaffold. They show a solvent-
dependent pyrene-like fluorescence which may be of interest
0
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for various applications. Furthermore,
a
synthesized
tripyrenyladamantane is able to reversibly bind and release
chloroform in the solid state. Future work will consist of
derivatization of the synthesized pyrenyladamantanes and
testing their ability to bind various guests in the solid state.
Figure 4. Crystal packing of 7 viewed in [100] direction. Pyrene
I, II and III are highlighted in red, blue and green. The disordered
molecules of chloroform occupy channels highlighted in yellow.
EXPERIMENTAL SECTION
General Remarks. Solvents were purified prior to use by
reported methods. All reagents were purchased from Sigma-
Aldrich and used without further purification. The reaction
progress was monitored by means of thin-layer chromatog-
raphy (TLC) which was performed on aluminum foil plates
covered with silica gel 60 F254. Column chromatography was
performed on silica gel 60 (0.040–0.063 mm, 230-400 mesh,
Analysis of intermolecular interactions in the crystal of 7
shows that pyrene II and III moieties are involved in a partial
π-π stacking with their inversion-related counterparts (inter-
ꢓꢐꢏꢛ ꢌꢐꢔꢕꢁꢏcꢒꢔ ꢁꢓꢒ ꢒqꢜꢁl ꢕꢋ ꢉ.ꢇꢈꢅ(ꢇ) Å ꢗꢋꢓ pꢖꢓꢒꢏꢒꢔ II ꢁꢏꢌ
ꢉ.ꢇ8ꢆ(5) Å for pyrenes III. On the other hand pyrene I, is
…
1
13
involved in a C10 – H10
π ꢔꢕꢁcꢃꢐꢏꢛ ꢐꢏꢕꢒꢓꢁcꢕꢐꢋꢏ ꢙꢐꢕh ꢕhꢒ
Fluka). H and C NMR spectra were recorded in CDCl on a
3
1
adamantane core of the inversion-related molecule. The dis-
tance between the planes of the symmetry-related pyrenes in
that case is as long as 5.318(4) Å (Fꢐꢛꢜꢓꢒ 5).
Bruker ARX 600 MHz (600 MHz for H and 151 MHz for
C). Chemical shifts were referenced relative to solvent sig-
1
3
1
13
nals: δ = 7.26 ppm for H and δ = 77.00 ppm for C. Spectra
were recorded at room temperature (291 K), chemical shifts
are presented in ppm, and coupling constants are presented in
Hz. Electronic absorption spectra were run on a Perkin Elmer
Lambda 45 UV/Vis spectrometer. Corrected emission spectra
were obtained on a Perkin Elmer LS55 Fluorescence spec-
trometer. The emission quantum yields were determined for
argon-purged solutions using quinine sulfate in 0.5 M sulfuric
acid (Φ = 0.546) as a reference.
F
General procedure for synthesis of 2-7. Alkylating agent RX
(for amounts of reactants, see Table 1 (S1) or S2) and TfOH
were added to a solution of pyrene in 10 ml CH Cl at room
2
2
temperature. After stirring for 5 min to 6 h (Table 1 (S1), S2),
the reaction mixture was poured into water (100 mL) and
extracted several times with dichloromethane. The combined
extracts were dried over anhydrous Na SO and evaporated to
2
4
dryness. The crude products were purified by column chroma-
tography on silica gel (hexane or petroleum ether/ ethyl ace-
tate as eluent) to gave the desired products.
2
-tert-butylpyrene (2). Purification by chromatography elut-
ing with petroleum ether/ethyl acetate (95/5, v/v) gave 2 (248
mg, 96% (Table S2, Entry 2)) as a white powder. mp 110-111
1
3
1
Figure 5. The most important intermolecular interactions formed
by 7 in the crystal structure viewed along [100]. Interatomic
distances shorter than the sum of the Van der Waals radii present-
ed as red dashed lines.
°C (lit. mp 110-112 °C). H NMR (600 MHz, CDCl ) δ 8.27
3
(s, 2H), 8.18 (d, J = 7.8 Hz, 2H), 8.10 (d, J = 8.7 Hz, 2H), 8.08
(
d, J = 8.7 Hz, 2H), 8.00 (t, J = 7.8 Hz, 1H), 1.64 (s, 9H);
1
3
1
C{ H} NMR (151 MHz, CDCl ) δ ꢄꢇ8.ꢆ, ꢄꢉꢈ.ꢆ, ꢄꢉ0.9,
3
1
27.5, 127.2, 125.5, 124.7, 124.6, 122.9, 122.1, 35.2, 31.9. MS
The transformation of the crystals of 7 into a powder is caused
by the loss of the chloroform guest, which apparently stabilize
the crystal structure. Therefore, this compound is able to bind
chloroform in its crystal structure in chloroform solution and
+
+
(EI): m/z: 259 [M] , 281 [M + Na] ; Anal. calcd. for C H : C,
2
0
18
92.98; H, 7.02; found: C, 92.77; H, 6.91.
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2
,7-di-tert-butylpyrene (3). Purification by chromatography
AUTHOR INFORMATION
1
2
3
4
5
6
7
8
9
eluting with petroleum ether/ethyl acetate (95/5, v/v) gave 3
(289 mg, 92% (Table S2, Entry 5)) as a white powder. mp
210-ꢅꢄꢅ °C (lit. mp 210-212 °C). H NMR (600 MHz,
CDCl ) δ 8.19 (s, 4H), 8.03 (s, 4H), 1.59 (s, 18H); C{ H}
NMR (151 MHz, CDCl ) δ 148.5, 130.8, 127.4, 122.8, 122.0,
3
calcd. for C H : C, 91.67; H, 8.33; found: C, 91.76; H, 8.20.
Corresponding Author
*E-mail: anna.wrona@chemia.uni.lodz.pl
1
4
1
1
3
1
3
ORCID
3
+
+
Anna Wrona-Piotrowicz: 0000-0001-6930-6989
Anna Makal: 0000-0001-9357-2670
Janusz Zakrzewski: 0000-0002-3403-1126
Notes
5.2, 31.9; MS (EI): m/z: 315 [M] , 337 [M + Na] ; Anal.
2
4
26
2
-(adamant-1-yl)pyrene (4). Purification by chromatography
eluting with hexane/ethyl acetate (95/5, v/v) gave 4 (312 mg,
3% (Table 1, Entry 1)) as a white powder. mp 218-ꢅꢄꢆ °C.
The authors declare no competing financial interest.
9
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
H NMR (600 MHz, CDCl ) δ 8.21 (s, 2H), 8.14 (d, J = 7.2
3
ACKNOWLEDGMENT
Financial support from the Polish National Science Centre ( NCN,
Grant Miniatura 2018/02/X/ST5/01472 ) is gratefully acknowl-
edged.
Hz, 2H), 8.07 (d, J = 9.0 Hz, 2H), 8.04 (d, J = 9.0 Hz, 2H),
7.96 (t, J = 7.2 Hz, 1H), 2.21 (s, 9H), 1.89 (s, 6H); C{ H}
NMR (151 MHz, CDCl ) δ 149.2, 131.0, 131.0, 127.6, 127.1,
1
Na] ; Anal. calcd. for C H : C, 92.81; H, 7.19; found: C,
9
2
1
3
1
3
+
25.4, 124.6, 123.0, 121.9; MS (EI): m/z: 337 [M] , 359 [M +
+
2
6
24
REFERENCES
2.67; H, 7.02.
,7-di(adamant-1-yl)pyrene (5). Purification by chromatog-
1. (a) Figueira-Duarte, T. M.; Müllꢒꢏ, K. Pyrene-based materials
for organic electronics. Chem. Rev. 2011, 111 (11), 7260-7314; (b)
Islam, M. M.; Hu, Z.; Wang, Q.; Redshaw, C.; Feng, X. Pyrene-based
aggregation-induced emission luminogens and their applications.
Mater. Chem. Front. 2019, 3, 762-781.
raphy eluting with hexane/ethyl acetate (95/5, v/v) gave 5 (447
mg, 95% (Table 1, Entry 5)) as a white pꢋꢙꢌꢒꢓ. ꢂp >ꢉꢈꢈ °C.
1
H NMR (600 MHz, CDCl ) δ 8.17 (s, 4H), 8.03 (s, 4H), 2.21
3
1
3
1
(s, 18H), 1.89 (s, 12H); C{ H} NMR (151 MHz, CDCl ): δ
3
2
. (a) Feng, X.; Hu, J.-Y.; Redshaw, C.; Yamato, T. Functionaliza-
148.8, 130.8, 127.4, 123.0, 121.6, 43.8, 36.9, 29.1; MS (EI):
m/z: 471 [M] , 493 [M + Na] ; Anal. calcd. for C H : C,
tion of pyrene to prepare luminescent materials-typical examples of
synthetic methodology. Chem. Eur. J. 2016, 22 (34), 11898-11916;
+
+
3
6
38
91.86; H, 8.14; found: C, 91.96; H, 8.01.
,3-bis(pyren-2-yl)adamantane (6). Purification by chroma-
tography eluting with hexane/ethyl acetate (90/10, v/v) gave 6
332 mg, 62% (Table 1, Entry 8)) as a white powder. mp 274-
(
b) Casas-Solvas, J. M.; Howgego, J. D.; Davis, A. P. Synthesis of
1
substituted pyrenes by indirect methods. Org. Biomol. Chem. 2014,
12 (2), 212-232; (c) Mochida, K.; Kawasumi, K.; Segawa, Y.; Itami,
K. Direct Arylation of Polycyclic Aromatic Hydrocarbons through
Palladium Catalysis. J. Am. Chem. Soc. 2011, 133 (28), 10716-10719;
(
1
ꢅ75 °C. H NMR (600 MHz, CDCl ) δ 8.31 (s, 4H), 8.15 (d, J
=
4
3
(
d) Ji, L.; Lorbach, A.; Edkins, R. M.; Marder, T. B. Synthesis and
7.8 Hz, 4H), 8.09 (d, J = 9.0 Hz, 4H), 8.06 (d, J = 9.0 Hz,
Photophysics of a 2,7-Disubstituted Donor–Acceptor Pyrene Deriva-
tive: An Example of the Application of Sequential Ir-Catalyzed C–H
Borylation and Substitution Chemistry. J. Org. Chem. 2015, 80 (11),
5658-5665;
H), 7.96 (t, J = 7.8 Hz, 2H), 2.11 (s, 2H), 2.57 (s, 2H), 2.36
13
1
(q, J = 12.0 Hz, 8H), 2.02 (s, 2H); C{ H} NMR (151 MHz,
CDCl ) δ 148.5, 131.1, 130.9, 127.6, 127.3, 125.5, 124.7,
124.6, 123.1, 121.9, 50.2, 43.0, 38.0, 36.1, 29.9; MS (EI): m/z:
537 [M] , 559 [M + Na] ; Anal. calcd. for C H : C, 93.89; H,
3
3
. (a) Feng, X.; Hu, J.-Y.; Iwanaga, F.; Seto, N.; Redshaw, C.;
Elsegood, M. R. J.; Yamato, T. Blue-emitting butterfly-shaped
1,3,5,9-tetraarylpyrenes: synthesis, crystal structures, and
+
+
4
2
32
6.01; found: C, 94.02; H, 5.88.
,3,5-tris(pyren-2-yl)adamantane (7). Purification by chro-
photophysical properties. Org. Lett. 2013, 15 (6), 1318-1321; (b)
Feng, X.; Hu, J.-Y.; Tomiyasu, H.; Seto, N.; Redshaw, C.; Elsegood,
M. R. J.; Yamato, T. Synthesis and photophysical properties of novel
butterfly-shaped blue emitters based on pyrene. Org. Biomol. Chem.
2013, 11 (48), 8366-8374; (c) Liu, R.; Ran, H.; Zhao, Z.; Yang, X.;
Zhang, J.; Chen, L.; Sun, H.; Hu, J.-Y. Synthesis and Optical Proper-
ties of Donor–Acceptor-Type 1,3,5,9-Tetraarylpyrenes: Controlling
Intramolecular Charge-ꢀꢓꢁꢏꢔꢗꢒꢓ Pꢁꢕhꢙꢁꢖꢔ bꢖ ꢕhꢒ Chꢁꢏꢛꢒ ꢋꢗ π-
Conjugation Directions for Emission Color Modulations. ACS Omega
2018, 3 (5), 5866-5875; (d) Maeda, H.; Hironishi, M.; Ishibashi, R.;
Mizuno, K.; Segi, M. Synthesis and fluorescence properties of dioxa-,
dithia-, and diselena-[3.3](1,3)pyrenophanes. Photochem. Photobiol.
Sci. 2017, 16 (2), 228-237.
1
matography eluting with hexane/ethyl acetate (85/15, v/v)
gave 7 (464 mg, 63% (Table 1, Entry 10)) as a white powder.
mp 221-ꢅꢅꢅ °C. H NMR (600 MHz, CDCl ) δ 8.42 (s, 6H),
8
9
=
6
1
1
3
.17 (d, J = 7.8 Hz, 6H), 8.12 (d, J = 9.0 Hz, 6H), 8.08 (d, J =
.0 Hz, 6H), 7.99 (t, J = 7.8 Hz, 3H), 2.86 (m, 1H), 2.82 (d, J
12.0 Hz, 3H), 2.75 (d, J = 12.6 Hz, 3H), 2.48 (d, J = 2.4 Hz,
1
3
1
H); C{ H} NMR (151 MHz, CDCl ) δ 147.8, 131.2-, 131.0,
3
27.6, 127.4, 125.6, 124.8, 124.5, 123.-3, 121.9, 49.4, 42.2,
+
+
39.2, 30.7; MS (EI): m/z: 737 [M] , 759 [M + Na] ; Anal.
calcd. for C H : C, 94.53; H, 5.47; found: C, 94.41; H, 5.35.
5
8
40
4
. (a) Peng, J.; Guo, X.; Jiang, X.; Zhao, D.; Ma, Y. Developing
efficient heavy-atom-free photosensitizers applicable to TTA
upconversion in polymer films. Chem. Sci. 2016, 7 (2), 1233-1237;
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for efficient triplet–triplet annihilation upconversion: annihilator-
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H and C NMR spectra, absorption and emission spectra and
(
86), 13111-13113; (d) Castellano, F. N.; McCusker, C. E. MLCT
photophysical data for compounds 2-7 (PDF)
Crystal structure data of compound 7 (CIF)
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1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
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3
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4
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0
1
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8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
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8
9
0
1
2
3
4
5
6
7
8
9
0
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