Fluorescence Enhancement of Aromatic Macrocycles by Lowering Excited Singlet State Energies

Article abstract of DOI:10.1021/acs.joc.9b02379

A series of cyclo-meta-phenylene congeners with a variation of interphenylene bridges was synthesized by adopting concise synthetic routes to investigate the structure-fluorescence relationships of macrocycles. With fundamental UV-vis absorption and fluor

Full text of DOI:10.1021/acs.joc.9b02379

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Article
Fluorescence enhancement of aromatic macrocycles
by lowering excited singlet state energies
Koki Ikemoto, Toshiki Tokuhira, Akari Uetani, Yu Harabuchi, Sota Sato, Satoshi Maeda, and Hiroyuki Isobe
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b02379 • Publication Date (Web): 06 Nov 2019
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Fluorescence enhancement of aromatic macrocycles by lowering excited singlet state energies
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Koki Ikemoto,†,‡ Toshiki Tokuhira,† Akari Uetani,§ Yu Harabuchi,§,∥,⊥ Sota Sato,†,‡ Satoshi Maeda,§,⊥,#
Hiroyuki Isobe†,‡,*
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†Department of Chemistry, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033,
Japan
‡JST, ERATO Isobe Degenerate π-Integration Project, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033,
Japan
§Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku,
Sapporo 060-0810, Japan
∥JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan
⊥Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University,
Sapporo 001-0021, Japan
#Research and Services Division of Materials Data and Integrated System (MaDIS), National Institute
for Materials Science (NIMS), Tsukuba 305-0044, Japan
*E-mail: isobe@chem.s.u-tokyo.ac.jp
high
low
low
S1
φ
high
Abstract
A series of cyclo-meta-phenylene congeners with a variation of interphenylene bridges were
synthesized by adopting concise synthetic routes to investigate the structure-fluorescence relationships
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of macrocycles. With fundamental UV-vis absorption and fluorescence spectra, no unique effect of the
macrocyclic structures was noted. However, the fluorescence quantum yields were dramatically
affected by the macrocyclic structures and varied at a range of 5–92%. The quantum yields
qualitatively depended on the number of the vinylene-bridged phenanthrenylene panels, and the
theoretical investigations revealed the energetic and structural effects of the phenanthrenylene panels
during nanosecond photodynamic processes. A high energy barrier along the S0/S1-internal conversion
path to reach the minimum energy conical intersection (MECI) was necessary to hamper a non-
radiative process, and with the transition state energy level of the excited singlet state being insensitive
to macrocyclic structures, a low energy level of excited singlet states (S1MIN) was required to facilitate
efficient fluorescence.
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Introduction
Manipulating the fluorescence properties of organic molecules holds promise for the
development of optical/optoelectronic organic materials. A unique series of organic materials have
been designed simply by arraying aromatic panels in macrocyclic structures.1 For instance, the
circularly polarized luminescence of organic molecules was dramatically enhanced by an intense
magnetic transient dipole moment induced in belt-persistent macrocycles,2 and a magnetic-field-
induced enhancement of electroluminescence, i.e., a magneto-electroluminescence effect, was
observed with [n]cyclo-meta-phenylene ([n]CMP, n = 6; Figure 1) embedded in a single-layer organic
light-emitting device (OLED).3,4 Furthermore, a single-layer OLED with a high internal quantum
efficiency was fabricated by using solely hydrocarbon macrocycles including [3]cyclo-3,6-
phenanthrenylene ([3]CPhen3,6) as an efficient emitter. 5 , 6 However, the structural factors of
macrocycles for efficient fluorescence have not been elucidated. Specifically, [6]CMP is a poor emitter
with a photoluminescent quantum yield (f) of 6%, whereas its vinylene-bridged congener, [3]CPhen3,6,
is an excellent emitter with an efficient yield of f = 75% (Figure 1).6 However, our understanding of
the structure-fluorescence relationships of macrocycles is still immature, and the origins of such
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considerable differences in f values are unclear. In this study, we designed and synthesized a series of
[6]CMP-related macrocycles that differed in the number of phenylene/phenanthrenylene panels having
different degrees of π-conjugation and flexibility. The macrocycles also differed in their
photoluminescence quantum yields. With the aid of theoretical investigations, the energy levels of
excited singlet states were found to be important for facilitating the fluorescence of the macrocycles.
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[3]CPhen3,6
φ = 75%
[6]CMP
φ = 6%
Figure 1. Macrocyclic congeners with different bridges. The fluorescence of [6]CMP and its vinylene-
bridged congener, [3]CPhen3,6, is considerably different.
Results and discussion
Synthesis
The structures of the [6]CMP-related macrocycles were diversified by devising a concise,
two-step synthetic route. For the two-step synthesis to exploit structural variations between [6]CMP
and [3]CPhen3,6, three types of coupling components (1a-1c) were designed with two phenylene units
differing in-between bridges (Scheme 1). Two different coupling components were then assembled
into a linear precursor 3 by Suzuki-Miyaura coupling between 1 and 2,7 and the macrocyclic structure
of a bridged [6]CMP congener 4 was completed by a subsequent Yamamoto-type coupling reaction.8,9
Six macrocycles with different bridging structures (4a-4f) were thus prepared in moderate yields.
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Scheme 1. Two-step synthesis of [6]CMP-related macrocycles
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1a: X = Br
2a: X = Bpin
step i
step ii
X
X
O O
PdCl2(dppf)
•CH2Cl2
K2CO3
Ni(cod)2
cod
2,2'-bipyridine
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O
O
1b: X = Br
2b: X = Bpin
1 + 2
3
4
DMSO
80 ºC
toluene/DMF
80 ºC
X
X
X
X
Br
Br
1c: X = Br
2c: X = Bpin
O O
O O
O
O
O
O
4a
4b
4c
4d
4e
4f
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
70% (i)
25% (ii)
56% (i)
34% (ii)
21% (i)
32% (ii)
39% (i)
56% (ii)
26% (i)
59% (ii)
65% (i)
34% (ii)
Other relevant compounds were synthesized by adopting different methods. One-pot
cyclization of dibromide 1b with a Yamamoto-type coupling reaction afforded a macrocycle (4g)
furnished with three methylene/acetal bridges (Scheme 2a).6, 10 Macrocycle 6 was designed by
replacing one two-phenylene unit with one alkane chain. Macrocycle 6 was synthesized from 1,5-
hexadiene, which was hydroborylated and coupled with 1a for the final Ni-mediated cyclization
(Scheme 2b).
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Scheme 2. Synthesis of [6]CMP-related compounds
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6
(a)
O O
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O
O
Ni(cod)2
cod
2,2’-bipyridine
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1b
4g
toluene/DMF
80 ºC
O
O
O
O
O
O
O
O
27%
(b)
1) 9-BBN
2) 1a
Pd(PPh3)4
NaOH
5
THF/H2O
rt to 65 ºC
Br Br
31%
Ni(cod)2
cod
2,2’-bipyridine
6
toluene/DMF
65 ºC
77%
Photophysical properties
We first measured the UV-vis absorption spectra of the macrocycles and reference compounds.
The onset absorption peaks are listed in Table 1 (see also Figure S1 for the spectra).11 In the presence
of phenanthrenylene panels, the absorptions were red-shifted. The observations should be due to the
effects of π-extension via vinylene bridges, because the π-extension should narrow the HOMO-LUMO
gap and, consequently, lower the excited state energy level (see below). We then measured the
fluorescence spectra. As expected, we also observed red-shifted fluorescence peaks with π-extended
congeners (Table 1 and Figure S1). However, when we measured the f values of the fluorescence, we
unexpectedly observed considerable differences among these molecules. Thus, the macrocycles with
two or more phenanthrenylene panels exhibited high f values above 60% ([3]CPhen3,6, 4a, 4b and 6),
and the macrocycles without phenanthrenylene panels exhibited low f values less than 10% (4e, 4f
and 4g). The highest f value was 92% with 4b, which surpassed the previous value of fluorescent
[3]CPhen3,6 (75%). A borderline case was the macrocyles with one phenanthrenylene panel:
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macrocycle 4d with one vinylene bridge was a poor emitter with f = 27%, and macrocycles 4c with
one vinylene bridge and two methylene/acetal bridges was a good emitter with f = 63%.
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Table 1. Photophysical data. See Figure S1 for the spectra.
labs,onset (nm) labs,max (nm), (ε)
l
em (nm)
f c
[3]CPhen3,6
395 a
402 a
392 a
392 a
371 a
323 b
319 b
333 a
317 b
377 a
323 (47,000), 336 (74,000), 375 (14,000) a 396, 419, 445 a 75% a
307 (38,000), 321 (51,000), 366 (10,000) a 398, 421, 447 a 78% a
4a
4b
315 (41,000), 355 (12,000) a
339 (22,000), 353 (16,000) a
333 (17,000), 343 (12,000) a
260 (14,000) b
391, 414, 438 a 92% a
4c
388 a
63% a
27% a
5% b
5% b
8% a
6% b
60% a
4d
382, 393 a
347, 355 b
351 b
4e
4f
255 (12,000) b
4g
300 (15,000) a
343, 356 a
337, 348 b
376 a
[6]CMP
6
251 (81,000) b
336 (24,000) a
phenanthrene 349 a
295 (12,000) a
350, 367, 386 a 15% a
a Solvent = toluene. b Solvent = CHCl3. c Absolute photoluminescence quantum yields were measured
on Hamamatsu Photonics C9920-02G.
Theoretical calculation
Experimentally, the photoluminescence decay of [3]CPhen3,6 was first measured to find a
nanosecond-order decay (6.5 nsec) (Figure S2). To gain insights into such nanosecond processes, we
then investigated relevant excited-state processes of two representative macrocycles, [6]CMP and
[3]CPhen3,6, with time-dependent density functional theory (TDDFT). In principle, the excited energy
gained at the S1 excited state is consumed via two paths leading to the S0 ground state, i.e., a radiative
path and a non-radiative path, and the non-radiative path is further categorized into two paths: an S0/S1-
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internal conversion path and singlet-triplet intersystem crossing path. In an internal conversion process,
nonadiabatic transitions take place efficiently in conical intersection (CI) regions where two electronic
states are energetically degenerate.12 The lowest energy point within a CI hyperspace, i.e. a minimum
energy CI (MECI), is optimized as a representative geometry of a CI region. In a series of
investigations, a pivotal role of S0/S1-internal conversion path has been disclosed for small
polyaromatic hydrocarbons (PAHs) by theoretical explorations of the MECIs between the ground and
first singlet excited electronic states (S0/S1-MECIs).13 However, the applicability of such theoretical
models to large molecular materials cannot be taken granted and must be examined at the cost of
computational tasks involving many branching paths. In this study, with recent development of
automated search protocols adopting the single component-artificial force induced reaction (SC-AFIR)
method14,15 as well as the energy shift (ES)/TDDFT method,16 we succeeded in locating S0/S1-MECIs
of [6]CMP (60 atoms) and [3]CPhen3,6 (66 atoms): there existed 41 S0/S1-MECIs with [6]CMP and 14
S0/S1-MECIs with [3]CPhen3,6 (Figures S42-S43). Unique structural features of the S0/S1-MECIs were
commonly found with [6]CMP and [3]CPhen3,6. Among multiple arylene panels in the macrocycles,
only one panel was structurally deformed at the S0/S1-MECIs, and the deformed structures resembled
those of small PAHs with sp3-like deformation localized at one carbon atom (Figure S41).13
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The S0/S1-internal conversion path was further clarified by allocating the transition state (S1TS
)
on the S1 surface. The most preferred S0/S1-paths are shown in Figure 2a and 2b, respectively, for
[6]CMP and [3]CPhen3,6. The S1TS connecting two minima at the S1 state near the Frank-Condon region
(S1MIN) and S0/S1-MECI was located for [6]CMP to reveal an energy barrier of DE‡ = 0.42 eV (Figure
2a). The same internal conversion path was also clarified for [3]CPhen3,6 to reveal the energy barrier
of DE‡ = 1.4 eV (Figure 2b). Due to the late transition state for both molecules, the structural
deformations at the transition state were similar to those at the S0/S1-MECI. The deformations at the
transition state were therefore localized on a single panel, which resulted in the similar levels of the
S1TS energies relative to the S0MIN ground state (5.24 eV for [6]CMP vs. 5.00 eV for [3]CPhen3,6).17
Consequently, the energy barrier of the non-radiative S0/S1-internal conversion is largely determined
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by the S1MIN level. The S1MIN energy level of [3]CPhen3,6 was 1.22 eV lower than that of [6]CMP, and
the lower S1MIN level of [3]CPhen3,6 is understood by the stabilization of the π-π* state via the
delocalization of π and π* orbitals: The delocalization in [3]CPhen3,6 is more pronounced by the
extended π-conjugation than that in [6]CMP. The observation is consistent with that found in the
previous studies.13,18
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(a)
(b)
S1TS
5.24 eV
S1TS
5.00 eV
S0/S1-MECI
5.00 eV
S1MIN
4.82 eV
ΔE‡ =
0.42 eV
S0/S1-MECI
4.30 eV
S1MIN
ΔE‡ =
1.40 eV
nonradiative
decay
3.60 eV
fluorescence
S0MIN
S0MIN
Figure 2. Schematic pictures of the energetically most preferred internal conversion path for
macrocycles, (a) [6]CMP and (b) [3]CPhen3,6. The energy levels of S1MIN, S1TS and S0/S1-MECI at
the TDDFT level are shown relative to S0MIN in eV.
Finally, the S1MIN energy levels were theoretically located for all the macrocycles to reveal
qualitative correlations with the experimental f values. The S1MIN structures for 4a-4g, 6 and
phenanthrene were thus obtained by an identical TDDFT method, and the S1MIN energies relative to
the S0MIN energy were plotted against the experimental f values (Figure 3). Macrocycles with S1MIN
located above 3.6 eV reached f values of >70%, and the highest f value of 92% was achieved by 4b
with S1MIN = 3.7 eV.19 The plot qualitatively showed that a higher level of S1MIN above 4 eV resulted
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in poor fluorescence, partly because the S1TS levels were not much affected by the molecular structures;
the higher the S1MIN is, the lower the potential energy barrier gets along the internal conversion path.13
As can be found with 4c and 4d, the S1MIN at approximately 4 eV should be the borderline, which
requires in-depth analysis of S1TS level for speculation about the fluorescence efficiency. In-depth
understanding of another important non-radiative path, i.e., intersystem crossing path, should further
allow us predict the fluorescence efficiency in a more quantitative manner, which is of current interest
for the state-of-the-art theoretical investigations.
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100
4b
80
4a
[3]CPhen3,6
4c
60
40
20
0
6
4d
phenanthrene
4g
[6]CMP
4e
4f
3.0
3.5
4.0
1MIN (eV)
4.5
5.0
S
Figure 3. Correlations between the f values and the S1MIN levels.
Conclusions
We designed and synthesized a series of macrocycles by assembling phenanthrenylene-related
panels, which allowed us to explore the structure-fluorescence relationships of the macrocycles.
Among the 10 congeners, one congener with two phenanthrenylene panels and two phenylene panels
achieved a remarkable fluorescence quantum yield of 92%. Although we observed the expected red-
shifts in UV-vis absorption and fluorescence spectra, the quantum yields of fluorescence unexpectedly
varied. With the aid of theoretical studies and the adoption of the state-of-the-art analysis of
nanosecond dynamics, we found that the energy barriers for the non-radiative processes determined
the quantum yields. With the S1TS levels maintained throughout the macrocyclic congeners, the S1MIN
levels decided the energy barrier height along the S0/S1-internal conversion path. Consequently,
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lowering S1MIN level facilitates the efficient fluorescence. We believe that the structure-fluorescence
relationships, together with mechanistic insights, can help the future development of fluorescent
macrocycles and that optoelectronic macrocyclic materials can be generated to be used in devices.
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Experimental section
General. All the reactions were performed under N2 atmosphere. An oil bath was used to
elevate the temperature of reactions. Flash silica gel column chromatography was performed on silica
gel 60N (spherical and neutral gel, 40–50 µm, Kanto). Gel permeation chromatography (GPC) was
performed on a Japan Analytical Industry LC-9104 with JAIGEL 1H-40, 2H-40, and 2.5H-40
polystyrene columns (40 mm i.d. ´ 600 mm) and chloroform as the eluent. Analytical high pressure
liquid chromatography (HPLC) was performed on a JASCO LC-2000 Plus series systems with a
COSMOSIL 5C18-MS-II column (4.6 mm i.d. ´ 250 mm) and a COSMOSIL π-NAP column (4.6 mm
i.d. ´ 250 mm) with a flow rate of 1.0 mL/min and temperature of 40 °C in a column oven (JASCO
CO-2060PLUS) while under observation with a UV-vis detector (JASCO MD2018PLUS). Proton (1H)
and carbon (13C) NMR spectra were recorded at 298 K on a JEOL RESONANCE JNM-ECA II 600
equipped with the UltraCOOL probe. Chemical shift values are given in ppm with relative to residual
solvent signals of chloroform (1H NMR: δ 7.26; C NMR: δ 77.2). Data are reported as follows:
13
chemical shift, multiplicity (s = singlet, brs = broad singlet, d = doublet, t = triplet, m = multiplet),
coupling constant in hertz (Hz) and a relative integration value. High-resolution mass spectrometry
was performed on a Bruker micrOTOF II spectrometer equipped with an APCI probe. Elemental
analyses were performed on an ELEMENTAR Vario MICRO cube (Elemental Analysis Center, School
of Science, The University of Tokyo). As was the case with large macrocycles,4,10 removal of solvent
was not feasible with the present macrocycles. Ultraviolet-visible (UV) spectra were recorded on a
JASCO V-670 spectrometer. Fluorescence spectra were recorded on a JASCO FP-8500
spectrophotometer. Absolute fluorescence quantum yields were determined on a Hamamatsu
Quantaurus-QY C11347.
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Anhydrous THF, DMF and toluene were purified by a solvent purification system
(GlassContour) equipped with columns of activated alumina and supported copper catalyst (Q-5). The
3,6-dibromophenanthrene (1a) 20 and compound 1b 21 were synthesized according to literature
procedures.
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Synthesis.
3,6-Diborylphenanthrene 2a: A mixture of 3,6-dibromophenanthrene (1a) (1.00 g, 2.98
mmol), PdCl2(dppf)•CH2Cl2 (286 mg, 0.595 mmol), bis(pinacolato)diboron (2.27 g, 8.93 mmol) and
potassium acetate (1.46 g, 14.9 mmol) in 1,4-dioxane (30 mL) was stirred at 80 ºC for 15 h. After
addition of water (30 mL), the aqueous layer was extracted with CHCl3 (30 mL × 3), and the combined
organic layer was washed with brine (120 mL), dried over Na2SO4, and concentrated in vacuo. The
crude mixture was washed with MeOH (30 mL) to afford the title compound as an off-white powder
in 89% yield (1.14 g, 2.64 mmol). The spectra of 2a were identical to data found in the literature.22
Diboryl acetal 2b: A mixture of compound 1b (2.13 g, 4.70 mmol), PdCl2(dppf)•CH2Cl2 (192
mg, 0.235 mmol), bis(pinacolato)diboron (2.63 g, 10.4 mmol) and potassium acetate (2.77 g, 28.2
mmol) in 1,4-dioxane (47 mL) was stirred at 80 ºC for 20 h. After addition of water (50 mL), the
aqueous layer was extracted with CHCl3 (50 mL × 3), and the combined organic layer was washed
with brine (180 mL), dried over Na2SO4, and concentrated in vacuo. The crude mixture was washed
with MeOH (100 mL) to afford the title compound as an off-white powder in 94% yield (2.43 g, 4.42
mmol). 1H NMR (600 MHz, CDCl3) δ 8.41 (s, 2H), 7.87 (d, J = 7.5, 0.9 Hz, 2H), 7.74 (d, J = 7.5 Hz,
2H), 4.20 (brs, 4H), 3.65 (brs, 4H), 1.39 (s, 24H); 13C{1H} NMR (150 MHz, CDCl3) δ 135.6, 135.3,
132.7, 130.6, 125.4, 92.8, 84.2, 61.6, 25.0 (A signal for the carbon nuclei bonded to the boron nuclei
was not observed due to the quadrupolar relaxation induced by the boron nuclei.); HRMS (APCI/TOF)
m/z [M + H]+ calcd for C30H39B2O8 549.2826, found 549.2831.
3,3’-Diboryl-1,1’-biphenyl (2c): A mixture of 3,3’-dibromo-1,1’-biphenyl (1c) (3.12 g, 10.0
mmol), PdCl2(PPh3)2 (351 mg, 0.500 mmol), bis(pinacolato)diboron (5.59 g, 22.0 mmol) and
potassium acetate (4.91 g, 50.0 mmol) in DMSO (50 mL) was stirred at 80 ºC for 18 h. After addition
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of water (80 mL), the precipitate was collected by filtration and washed with water (20 mL). The solid
was dissolved in AcOEt (80 mL), and the organic layer was washed with brine (100 mL), dried over
Na2SO4, and concentrated in vacuo. The crude mixture was purified by silica gel column
chromatography (eluent: AcOEt:hexane = 1:10) to afford the title compound as an off-white powder
in 97% yield (3.96 g, 9.74 mmol). Spectra of 2c were identical to data found in the literature.23
Two-step Syntheses of [6]CMP-related Macrocycles.
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5,10
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bis(6
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bromophenanthren
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yl)
‐
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‐
tetraoxapentacyclo[12.4.4.01,14.02,7.08,13]docosa‐2(7),3,5,8(13),9,11‐hexaene (Precursor 3a): A
mixture of diboryl acetal 2b (206 mg, 0.376 mmol), 3,6-dibromophenanthrene (1a) (631 mg, 1.88
mmol), PdCl2(dppf)•CH2Cl2 (30.7 mg, 0.0376 mmol) and potassium carbonate (260 mg, 1.88 mmol)
in DMSO (7.5 mL) was stirred at 80 ºC for 24 h. After addition of water (15 mL), the resulting
precipitate was collected by filtration and washed with water (10 mL) and MeOH (10 mL). The crude
material was purified by silica gel column chromatography (eluent: chloroform) and gel permeation
chromatography to afford the title compound in 70% yield (211 mg, 0.262 mmol) as a white solid. Rf
= 0.59 (chloroform); 1H NMR (600 MHz, CDCl3) δ 8.88 (d, J = 1.8 Hz, 2H), 8.82 (d, J = 1.2 Hz, 2H),
8.37 (d, J = 1.5 Hz, 2H), 8.00 (d, J = 8.1 Hz, 2H), 7.98 (d, J = 8.1 Hz, 2H), 7.94 (dd, J = 8.1, 1.2 Hz,
2H), 7.87 (dd, J = 8.1, 1.5 Hz, 2H), 7.79 (d, J = 8.7 Hz, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.71 (d, J = 8.7
Hz, 2H), 7.69 (dd, J = 8.4, 1.8 Hz, 2H), 4.33 (brs, 4H), 3.81 (brs, 4H); 13C NMR (150 MHz, CDCl3,
298 K) δ 143.4, 139.7, 133.7, 132.5, 131.9, 131.8, 131.0, 130.3, 130.1, 129.6, 129.4, 128.6, 127.2,
127.2, 126.9, 126.8, 125.8, 123.7, 121.6, 121.2, 92.9, 61.7. HRMS (APCI/TOF) m/z [M + H]+ calcd
for C46H31Br2O4 805.0584, found 805.0560.
27,30,39,42
‐
‐
Tetraoxadodecacyclo[20.12.4.426,31.22,5.28,11.212,15.218,21.04,9.014,19.025,37.026,31.032,36]pentaconta
1(35),2,4,6,8,10,12,14,16,18,20,22(38),23,25(37),32(36),33,43,45,47,49‐icosaene (Macrocycle 4a):
After stirring mixture of 2,2’-bipyridine (168 mg, 1.08 mmol), 1,5-cyclooctadiene (132 µL, 10.8
mmol) and bis(1,5-cyclooctadiene)nickel(0) (296 mg, 1.08 mmol) in a mixture of toluene (2.3 mL)
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and DMF (2.3 mL) at 80 ºC for 30 min, a solution of precursor 3a (109 mg, 0.135 mmol) in toluene (9
mL) was added dropwise over 1 h. The mixture was stirred at 80 °C for an additional 1 h. After the
reaction mixture was cooled down to ambient temperature, water (13 mL) was added, and the mixture
was stirred vigorously overnight. The precipitate was collected by filtration and washed with water
(10 mL) and MeOH (10 mL). Recrystallization from o-dichlorobenzene gave the title compound in
25% yield (23 mg, 0.034 mmol) as a white solid. 1H NMR (600 MHz, CDCl3) δ 9.93 (s, 2H), 9.80 (s,
2H), 9.12 (s, 2H), 8.24 (dd, J = 7.8, 1.8 Hz, 2H), 8.14 (dd, J = 8.4, 1.8 Hz, 2H), 8.10 (dd, J = 8.1, 1.8
Hz, 2H), 8.01 (d, J = 7.8 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H), 7.91 (d, J = 8.1 Hz, 2H), 7.78 (d, J = 8.7
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Hz, 2H), 7.77 (d, J = 8.7 Hz, 2H), 4.32 (brs, 4H), 3.78 (brs, 4H); The C NMR spectrum was not
obtained owing to low solubility of the title compound; HRMS (APCI/TOF) m/z [M + H]+ calcd. for
C46H31O4 647.2217, found 647.2198. Anal. Calcd for (C46H30O4)1(C6H4Cl2)0.1: C 84.62, H 4.63, Cl
1.07. Found, C 84.45, H 4.70, Cl 1.26. The assignment is supported by an X-ray crystallographic
structure determination.
3 ‐ Bromo ‐ 6 ‐ [3' ‐ (6 ‐ bromophenanthren ‐ 3 ‐ yl) ‐ [1,1' ‐ biphenyl] ‐ 3 ‐
yl]phenanthrene (Precursor 3b): Following the procedure to prepare 3a, a reaction mixture of 2c (406
mg, 1.00 mmol) and 1a (1.68 g, 5.00 mmol) afforded the title compound in 56% yield (370 mg, 0.556
mmol) as a white solid. Rf = 0.31 (chloroform/hexane = 1:4); 1H NMR (600 MHz, CDCl3) δ 8.90 (d,
J = 1.8 Hz, 2H), 8.84 (d, J = 1.2 Hz, 2H), 8.08 (dd, J = 1.5, 1.5 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H), 7.97
(dd, J = 8.4, 1.2 Hz, 2H), 7.82 (ddd, J = 8.4, 1.5, 1.5 Hz, 2H), 7.80 (d, J = 9.0 Hz, 2H), 7.79-7.77 (m,
4H), 7.72-7.67 (m, 6H); 13C{1H} NMR (150 MHz, CDCl3) δ 142.2, 142.2, 140.0, 132.0, 131.6, 131.0,
130.4, 130.1, 129.7, 129.7, 129.4, 127.2, 127.0, 127.0, 126.9, 126.8, 126.6, 125.7, 121.5, 121.1; HRMS
(APCI/TOF) m/z [M + H]+ calcd for C40H25Br2 663.0318, found 663.0308.
Nonacyclo[20.8.4.22,5.28,11.112,16.117,21.04,9.025,33.028,32]tetraconta
‐
1(31),2,4,6,8,10,12(36),13,15,17,19,21(35),22(34),23,25(33),26,28(32),29,37,39‐
icosaene (Macrocycle 4b): Following the reaction procedure to prepare 4a, the macrocyclization of 3b
(263 mg, 0.396 mmol) afforded the title compound in 34% yield (69.7 mg, 0.135 mmol) as a white
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solid after the purification by recrystallization from o-dichlorobenzene. 1H NMR (600 MHz, CDCl3)
δ 9.87 (s, 2H), 9.64 (s, 2H), 8.65 (s, 2H), 8.25 (dd, J = 8.3, 1.5 Hz, 2H), 8.08 (dd, J = 8.1, 1.8 Hz, 2H),
8.06 (d, J = 8.3 Hz, 2H), 8.03 (d, J = 8.1 Hz, 2H), 7.95 (d, J = 7.8 Hz, 2H), 7.82 (s, 4H), 7.73 (d, J =
7.8 Hz, 2H), 7.65 (dd, J = 7.8, 7.8 Hz, 2H); The 13C NMR spectrum was not obtained owing to low
solubility of the title compound; HRMS (APCI/TOF) m/z [M + H]+ calcd for C40H25 505.1951, found
505.1939. Anal. Calcd for (C40H24)1(C6H4Cl2)0.07: C 94.29, H 4.75, Cl 0.96. Found, C 94.26, H 4.70,
Cl 0.97.
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‐
Bromo
‐
10
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(6
‐
{10
‐
bromo
‐
15,18,19,22
‐
tetraoxapentacyclo[12.4.4.01,14.02,7.08,13]docosa ‐ 2(7),3,5,8(13),9,11 ‐ hexaen ‐ 5 ‐
yl}phenanthren ‐ 3 ‐ yl) ‐ 15,18,19,22 ‐ tetraoxapentacyclo[12.4.4.01,14.02,7.08,13]docosa ‐
2(7),3,5,8(13),9,11‐hexaene (Precursor 3c): Following the procedure to prepare 3a, a reaction
mixture of 2a (100 mg, 0.233 mmol) and 1b (528 mg, 1.16 mmol) afforded the title compound in 21%
1
yield (44 mg, 0.048 mmol) as a white solid. Rf = 0.20 (chloroform); H NMR (600 MHz, CDCl3) δ
8.98 (s, 2H), 8.19 (d, J = 1.4 Hz, 2H), 8.15 (d, J = 1.6 Hz, 2H), 8.05 (d, J = 8.4 Hz, 2H), 7.92 (dd, J =
8.4, 1.2 Hz, 2H), 7.91 (d, J = 7.8 Hz, 2H), 7.87 (dd, J = 7.8, 1.4 Hz, 2H), 7.85 (s, 2H), 7.66 (d, J = 8.4
13
Hz, 2H), 7.56 (dd, J = 8.4, 1.6 Hz, 2H), 4.24 (brs, 8H), 3.69 (brs, 8H); C{1H} NMR (150 MHz,
CDCl3) δ 143.7, 139.2, 135.2, 132.5, 132.4, 132.3, 132.0, 131.9, 130.7, 129.5, 129.0, 128.4, 127.3,
127.2, 127.1, 126.5, 124.6, 123.6, 121.7, 92.6 (2C), 61.6 (2C); HRMS (APCI/TOF) m/z [M + H]+ calcd
for C50H37Br2O8 923.0850, found 923.0854.
7,10,31,34,43,46,53,56
‐
Octaoxatetradecacyclo[24.12.4.46,11.430,35.22,5.212,15.216,19.222,25.04,13.06,11.018,23.029,41.030,35.036,40]octap
entaconta ‐ 1(39),2,4,12,14,16,18,20,22,24,26(42),27,29(41),36(40),37,47,49,51,57 ‐ nonadecaene
(Macrocycle 4c): Following the reaction procedure to prepare 4a, the macrocyclization was performed
using 3c (191 mg, 0.207 mmol). The crude mixture was washed with boiling o-dichlorobenzene (50
mL), and the residue was then extracted with boiling nitrobenzene (100 mL). After evaporation of
nitrobenzene, the material was washed with CHCl3 (10 mL) to afford the title compound in 32% yield
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(55 mg, 0.067 mmol) as a white solid. 1H NMR (600 MHz, CDCl3) δ 9.65 (s, 2H), 9.03 (s, 2H), 8.91
(s, 2H), 8.17 (d, J = 8.4, 1.8 Hz, 2H), 8.11 (d, J = 8.1, 1.5 Hz, 2H), 8.03 (d, J = 7.8 Hz, 2H), 8.01 (d, J
= 8.1, 1.5 Hz, 2H), 7.93 (d, J = 7.8 Hz, 2H), 7.91 (d, J = 8.4 Hz, 2H), 7.82 (s, 2H), 4.30 (brs, 8H), 3.78
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(brs, 8H); The C NMR spectrum was not obtained owing to low solubility of the title compound;
HRMS (APCI/TOF) m/z [M + H]+ calcd for C50H37O8 765.2483, found 765.2504; Anal. Calcd for
(C50H36O8)1(C6H5NO2)0.4: C 77.31, H 4.71, N 0.69. Found, C 77.01, H 4.62, N 0.68.
3,6‐Bis({3'‐bromo‐[1,1'‐biphenyl]‐3‐yl})phenanthrene (Precursor 3d): Following
the procedure to prepare 3a, a reaction mixture of 2a (186 mg, 0.432 mmol) and 1c (673 mg, 2.16
mmol) afforded the title compound in 39% yield (107 mg, 0.167 mmol) as a white solid. Rf = 0.41
(chloroform/hexane = 1:4); 1H NMR (600 MHz, CDCl3) δ 8.96 (d, J = 1.4 Hz, 2H), 8.02 (d, J = 7.7
Hz, 2H), 7.93 (d, J = 1.2 Hz, 2H), 7.90 (dd, J = 7.7, 1.4 Hz, 2H), 7.83 (dd, J = 2.4, 1.9 Hz, 2H), 7.82
(s, 2H), 7.81-7.78 (m, 2H), 7.66-7.60 (m, 6H), 7.51 (ddd, J = 8.1, 1.9, 1.1 Hz, 2H), 7.34 (dd, J = 8.1,
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8.1 Hz, 2H); C{1H} NMR (150 MHz, CDCl3) δ 143.4, 142.5, 140.6, 139.5, 131.8, 130.8, 130.6,
130.5 (2C), 129.7, 129.4, 127.5, 127.0, 126.7, 126.5, 126.4, 126.1, 123.1, 121.4; HRMS (APCI/TOF)
m/z [M + H]+ calcd for C38H25Br2 639.0318, found 639.0304.
Octacyclo[20.8.4.12,6.17,11.112,16.117,21.025,33.028,32]octatriaconta
‐
1(31),2(38),3,5,7,9,11(37),12(36),13,15,17,19,21(35),22(34),23,25(33),26,28(32),29 ‐ nonadecaene
(Macrocycle 4d): Following the reaction procedure to prepare 4a, the macrocyclization of 3d (102 mg,
0.159 mmol) afforded the title compound in 56% yield (43.0 mg, 0.0892 mmol) as a white solid after
1
the purification by recrystallization from o-dichlorobenzene. H NMR (600 MHz, CDCl3) δ 9.54 (s,
2H), 8.71 (s, 2H), 8.57 (s, 2H), 8.10 (dd, J = 8.3, 1.5 Hz, 2H), 8.02 (d, J = 8.3 Hz, 2H), 7.92 (d, J = 7.8
Hz, 2H), 7.84 (d, J = 7.2 Hz, 2H), 7.81 (s, 2H), 7.80 (d, J =7.8 Hz, 2H), 7.77 (d, J =7.8 Hz, 2H), 7.62
13
(dd, J = 7.8, 7.2 Hz, 2H), 7.61 (dd, J = 7.8, 7.2 Hz, 2H); The C NMR spectrum was not obtained
owing to low solubility; HRMS (APCI/TOF) m/z [M + H]+ calcd for C38H25 481.1951, found 481.1975;
Anal. Calcd for (C38H24)1(C6H4Cl2)0.01: C 94.83, H 5.03, Cl 0.15. Found, C 94.83, H 4.95, Cl 0.23.
5
‐
Bromo
‐
10
‐
(3'
‐
{10
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‐
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tetraoxapentacyclo[12.4.4.01,14.02,7.08,13]docosa‐2(7),3,5,8(13),9,11‐hexaen‐5‐yl}‐[1,1'‐
biphenyl] ‐ 3 ‐ yl) ‐ 15,18,19,22 ‐ tetraoxapentacyclo[12.4.4.01,14.02,7.08,13]docosa ‐
2(7),3,5,8(13),9,11‐hexaene (Precursor 3e): Following the procedure to prepare 3a, a reaction
mixture of 2c (203 mg, 0.500 mmol) and 1b (1.14 g, 2.50 mmol) afforded the title compound in 26%
yield (117 mg, 0.130 mmol) as a white solid. Rf = 0.25 (chloroform); 1H NMR (600 MHz, CDCl3) δ
8.11 (d, J = 1.6 Hz, 2H), 8.07 (d, J = 1.8 Hz, 2H), 7.90 (dd, J = 1.5, 1.5 Hz, 2H), 7.85 (d, J = 8.1 Hz,
2H), 7.74 (dd, J = 8.1, 1.8 Hz, 2H), 7.71 (ddd, J = 7.2, 1.5, 1.5 Hz, 2H), 7.67 (ddd, J = 7.8, 1.5, 1.5 Hz,
2H), 7.65 (d, J = 8.3 Hz, 2H), 7.62 (dd, J = 7.8, 7.2 Hz, 2H), 7.56 (dd, J = 8.3, 1.6 Hz, 2H), 4.23 (brs,
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8H), 3.69 (brs, 8H); C{1H} NMR (150 MHz, CDCl3) δ 143.3, 142.0, 141.5, 135.2, 132.4, 132.4,
132.2, 131.9, 129.6, 128.6, 128.3, 127.2, 127.1, 127.0, 126.7, 126.6, 124.5, 123.3, 92.6 (2C), 61.6
(2C); HRMS (APCI/TOF) m/z [M + H]+ calcd for C48H37Br2O8 899.0850, found 899.0872.
7,10,31,34,43,46,51,54
‐
Octaoxatridecacyclo[24.12.4.46,11.430,35.22,5.212,15.116,20.121,25.04,13.06,11.029,41.030,35.036,40]hexapentaco
nta ‐ 1(39),2,4,12,14,16(48),17,19,21,23,25(47),26(42),27,29(41),36(40),37,49,55 ‐ octadecaene
(Macrocycle 4e): Following the reaction procedure to prepare 4a, the macrocyclization of 3e (90 mg,
0.10 mmol) afforded the title compound in 59% yield (45 mg, 0.059 mmol) as a white solid after the
purification by silica gel column chromatography (eluent: chloroform) and gel permeation
chromatography. 1H NMR (600 MHz, CDCl3) δ 8.78 (s, 2H), 8.73 (s, 2H), 8.34 (s, 2H), 7.93 (dd, J =
8.1, 1.5 Hz, 2H), 7.89-7.88 (m, 6H), 7.83 (d, J = 7.2 Hz, 2H), 7.71 (d, J = 7.2 Hz, 2H), 7.60 (dd, J =
13
7.2, 7.2 Hz, 2H), 4.29 (brs, 8H), 3.77 (brs, 8H); C{1H} NMR (150 MHz, CDCl3) δ 142.2, 141.3,
140.3, 140.0, 133.6, 133.4, 133.1, 132.7, 129.7, 127.3, 127.2, 126.9, 126.6, 126.5, 126.3, 125.2, 122.7,
121.9, 93.0, 93.0, 61.7 (2C); HRMS (APCI/TOF) m/z [M + H]+ calcd for C48H37O8 741.2483, found
741.2485; Anal. Calcd for (C48H36O8)1(CHCl3)0.55(H2O)0.45: C 76.45, H 4.93, Cl 0.70. Found, C 76.13,
H 4.82, Cl 0.67.
5,10 ‐ Bis({3' ‐ bromo ‐ [1,1' ‐ biphenyl] ‐ 3 ‐ yl}) ‐ 15,18,19,22 ‐
tetraoxapentacyclo[12.4.4.01,14.02,7.08,13]docosa ‐ 2(7),3,5,8(13),9,11 ‐ hexaene (Precursor 3f):
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Following the procedure to prepare 3a, a reaction mixture of 2b (548 mg, 1.00 mmol) and 1c (1.56 g,
5.00 mmol) afforded the title compound in 65% yield (497 mg, 0.655 mmol) as a white solid. Rf = 0.52
(chloroform); 1H NMR (600 MHz, CDCl3) δ 8.18 (d, J = 1.6 Hz, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.79-
7.78 (m, 4H), 7.69 (dd, J = 7.8, 1.6 Hz, 2H), 7.65 (ddd, J = 7.2, 1.5, 1.5 Hz, 2H), 7.59-7.54 (m, 6H),
7.50 (d, J = 8.1 Hz, 2H), 7.32 (dd, J = 8.1, 7.8 Hz, 2H), 4.28 (brs, 4H), 3.75 (brs, 4H); 13C{1H} NMR
(150 MHz, CDCl3) δ 143.3, 143.0, 141.8, 140.6, 133.5, 132.4, 130.6, 130.5, 130.5, 129.6, 128.2, 127.1,
127.1, 126.7, 126.4. 126.0, 123.2, 123.1, 92.8, 61.6; HRMS (APCI/TOF) m/z [M + H]+ calcd for
C42H31Br2O4 757.0584, found 757.0586.
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27,30,39,42
‐
‐
Tetraoxadecacyclo[20.12.4.426,31.12,6.17,11.112,16.117,21.025,37.026,31.032,36]hexatetraconta
1(35),2(46),3,5,7,9,11(45),12(44),13,15,17,19,21(43),22(38),23,25(37),32(36),33 ‐ octadecaene
(Macrocycle 4f): Following the reaction procedure to prepare 4a, the macrocyclization of 3f (200 mg,
0.264 mmol) afforded the title compound in 34% yield (55 mg, 0.091 mmol) as a white solid after the
purification by recrystallization from o-dichlorobenzene. 1H NMR (600 MHz, CDCl3) δ 8.70 (s, 2H),
8.44 (dd, J = 1.8, 1.8 Hz, 2H), 8.40 (dd, J = 1.8, 1.2 Hz, 2H), 7.90-7.87 (m, 4H), 7.81-7.77 (m, 4H),
7.76-7.73 (m, 4H), 7.60 (dd, J = 7.8, 7.8 Hz, 2H), 7.59 (dd, J = 7.8, 7.8 Hz, 2H), 4.29 (brs, 4H), 3.77
(brs, 4H); 13C{1H} NMR (150 MHz, CDCl3) δ 141.5, 141.4, 141.4, 140.9, 140.0, 133.7, 132.5, 129.7,
127.1, 126.8, 126.4, 126.3, 126.0, 125.7, 125.6, 125.4, 123.0, 93.0 (A signal of the carbon nuclei in
the acetal group was not observed probably due to slow conformational change of the acetal group on
the NMR timescale.); HRMS (APCI/TOF) m/z [M + H]+ calcd for C42H31O4 599.2217, found
599.2231; Anal. Calcd for (C42H30)1(C6H4Cl2)0.05: C 83.83, H 5.02, Cl 0.58. Found, C 83.65, H 5.13,
Cl 0.29.
Synthesis of Other Relevant Macrocycles.
7,10,21,24,35,38,47,50,53,56,61,64
‐
Dodecaoxahexadecacyclo[28.12.4.46,11.420,25.434,39.22,5.212,15.216,19.226,29.04,13.06,11.018,27.020,25.033,45.034
,39.040,44]hexahexaconta ‐ 1(43),2,4,12,14,16,18,26,28,30(46),31,33(45),40(44),41,51,57,59,65 ‐
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octadecaene (Macrocycle 4g): After stirring a mixture of 2,2’-bipyridine (6.50 g, 41.6 mmol), 1,5-
cyclooctadiene (5.10 mL, 41.6 mmol) and bis(1,5-cyclooctadiene)nickel(0) (11.4 g, 41.6 mmol) in
toluene (330 mL) and DMF (330 mL) at 80 ºC for 30 min, a solution of compound 1b (9.00 g, 19.8
mmol) in toluene (1.32 L) was added dropwise over 1 h. The mixture was stirred at 80 °C for an
additional 1 h. After the reaction mixture was cooled to ambient temperature, water (2 L) was added,
and the mixture was stirred vigorously overnight. After extraction with toluene, the combined organic
layer was washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude material was
purified by silica gel column chromatography (eluent: chloroform) and gel permeation
chromatography. The material was washed with boiling PhCl (100 mL) and reprecipitated from
CHCl3/MeOH to give the title compound as a white solid in 27% yield (1.68 g, 1.78 mmol). 1H NMR
(600 MHz, CDCl3) δ 8.81 (d, J = 1.5 Hz, 6H), 7.98 (dd, J = 8.0, 1.5 Hz, 6H), 7.89 (d, J = 8.0 Hz, 6H),
4.28 (brs, 12H), 3.76 (brs, 12H); 13C{1H} NMR (150 MHz, CDCl3) δ 139.7, 133.8, 133.1, 127.3, 126.1,
121.8, 92.9, 61.7; HRMS (APCI/TOF) m/z [M + H]+ calcd for C54H43O12 883.2749, found 883.2724;
Anal. Calcd for (C54H42O12)1(CHCl3)0.55: C 69.07, H 4.52, Cl 6.17. Found, C 68.88, H 4.47, Cl 5.82.
1,6-Bis(6-bromophenanthren-3-yl)hexane (5): To a THF solution of 9-BBN (0.5 M; 0.500 mL,
0.250 mmol) was added 1,5-hexadiene (14.5 µL, 0.122 mmol) at ambient temperature, and the mixture
was stirred for 2 h. This solution was then transferred to a mixture of 3,6-dibromophenanthrene (1a)
(123 mg, 0.365 mmol) and Pd(PPh3)4 (123 mg, 7.30 µmol) in THF (2.5 mL) and 1.2 M NaOH aq. (0.6
mL, 0.730 mmol). After the reaction mixture was stirred at 65 ºC for 15 h, 1 M HCl aq. (4 mL) was
added. The aqueous layer was extracted with CHCl3, and the combined organic layer was washed with
water (4 mL) and brine (4 mL), dried over Na2SO4, and concentrated in vacuo. The crude mixture was
purified by gel permeation chromatography to give the title compound as a white solid in 31% yield
(23 mg, 0.038 mmol). 1H NMR (600 MHz, CDCl3) δ 8.80 (d, J = 1.8 Hz, 2H), 8.36 (s, 2H), 7.80 (d, J
= 7.7 Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 9.0 Hz, 2H), 7.66 (dd, J = 8.4, 1.8 Hz, 2H), 7.62
(d, J = 9.0 Hz, 2H), 7.46 (dd, J = 7.7, 1.5 Hz, 2H), 2.88 (t, J = 7.8 Hz, 4H), 1.79 (m, 4H), 1.49 (m,
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4H); 13C{1H} NMR (150 MHz, CDCl3) δ 141.9, 131.8, 130.9, 130.6, 130.2, 129.7, 129.4, 128.7, 128.4,
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127.4, 125.6, 125.5, 122.0, 120.7, 36.7, 31.9, 29.4; HRMS (APCI) m/z [M + H]+ calcd for C34H29Br2
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595.0631, found 595.0607.
Heptacyclo[16.8.4.22,5.28,11.04,9.021,29.024,28]tetratriaconta
‐
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1(27),2,4,6,8,10,18(30),19,21(29),22,24(28),25,31,33‐tetradecaene (Macrocycle 6): A mixture of
2,2’-bipyridine (625 mg, 4.00 mmol), 1,5-cyclooctadiene (490 µL, 4.00 mmol) and bis(1,5-
cyclooctadiene)nickel(0) (1.10 g, 4.00 mmol) in a mixture of toluene (8.3 mL) and DMF (8.3 mL) was
stirred at 65 ºC for 30 min. A solution of compound 5 (278 mg, 0.466 mmol) in toluene (33.4 mL) was
added dropwise to the mixture over 1 h, and the stirring was continued for an additional 1 h at 65 ºC.
After the reaction mixture was cooled down to room temperature, 1 M HCl aq. (60 mL) was added,
and the mixture was stirred vigorously overnight. The organic layer was washed with water (50 mL)
and brine (50 mL), dried over Na2SO4, and concentrated in vacuo. The crude material was purified by
silica gel column chromatography (eluent: chloroform) and gel permeation chromatography to afford
the title compound as a white solid in 77% yield (156 mg, 0.357 mmol). 1H NMR (600 MHz, CDCl3)
δ 9.42 (d, J = 1.4 Hz, 2H), 8.85 (s, 2H), 8.11 (dd, J = 8.0, 1.4 Hz, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.83
(d, J = 8.0 Hz, 2H), 7.75 (s, 4H), 7.46 (dd, J = 8.0, 1.5 Hz, 2H), 3.08 (t, J = 6.6 Hz, 4H), 2.14 (m, 4H),
13
1.81 (m, 4H); C{1H} NMR (150 MHz, CDCl3) δ 140.1, 138.2, 131.6, 130.7, 130.4, 130.4, 129.1,
129.1, 128.4, 127.0, 125.6, 124.6, 121.8, 119.3, 34.2, 29.9, 27.8; HRMS (APCI/TOF) m/z [M + H]+
calcd for C34H29 437.2264, found 437.2254; Anal. Calcd for C34H28: C 93.54, H 6.46. Found, C 93.29,
H 6.53.
Theoretical Calculations. The S0/S1-MECI geometries of [6]CMP and [3]CPhen3,6 were
searched by the following procedures. At the first, S0MIN geometries were systematically explored
using SC-AFIR method15 at the density-functional-based tight-binding (DFTB) level.24 Four and two
S0MIN geometries at the DFTB level were obtained for [6]CMP and [3]CPhen3,6, respectively. To search
for the guess geometries of S0/S1-MECIs, minimum energy seams of crossing geometries between the
ground singlet and triplet electronic states (S0/T1 -MESXs) were explored25 using the gradient
projection (GP)/SC-AFIR method14 at the DFTB level. In the S0/T1-MESX search, the initial
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geometries were set to the S0MIN geometries at the DFTB level, and the model collision energy
parameter for the SC-AFIR method was set to 100 kJ mol–1.26 This search automatically generates an
extensive list of guess structures. Then, S0/T1-MESXs which were energetically higher than the lowest
S0/T1-MESX by 1.0 eV or more were excluded from the list. The remaining S0/T1-MESXs were
reoptimized to the S0/S1-MECI geometries using energy shift (ES)27/TDDFT approach with an ES
value of 10.0 kJ/mol,16 where the average value of S0 and S1 energies on each S0/S1-MECI is shown
as the S0/S1-MECI energy in this paper.
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As the next step, the internal conversion paths on the S1 surface from S1MIN to S0/S1-MECI
regions were explored using the double-sphere AFIR (DS-AFIR) method. 28 To determine the
energetically most preferred S1TS, the locally updated planes (LUP) method29 was applied to all the
obtained DS-AFIR paths. Finally, the energetically most preferred S1TS, i.e. 5.24 eV for [6]CMP and
5.00 eV for [3]CPhen3,6, were determined. The reaction path through the most preferred S1TS was
verified by the intrinsic reaction coordinate (IRC) calculation. The ωB97XD functional30 with the 6-
31G(d) basis set (denoted by ωB97XD/6-31G(d)) was employed in DFT and TDDFT calculations, and
the solvent effect of toluene was evaluated using conductor-like polarizable continuum model
(CPCM).31 In the TDDFT calculations, Tamm-Dancoff approximation (TDA)32 was used.
To evaluate the S1MIN level shown in Figure 3, S0MIN geometries of each molecule were
explored using the SC-AFIR method15 at the DFTB24 level. Then, S1MIN geometries were searched by
optimizing the ten most stable S0MIN geometries at the TD-ωB97XD/6-31G(d) level. The solvent
effects were considered using CPCM,31 where toluene was adopted for [3]CPhen3,6, 4a, 4b, 4c, 4d, 4g,
6, and phenanthrene while chloroform was used for [6]CMP, 4e and 4f. In Figure 3, the energy of the
most stable S1MIN was shown relative to the most stable S0MIN
.
All the DFTB, DFT and TDDFT energies and gradients were computed using the Gaussian
09 and Gaussian 16 program packages.33 Also, the explorations of S0MIN, S1TS and S0/S1-MECI
geometries were done using the developmental version of GRRM program.34
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Supporting Information. The Supporting Information is available free of charge via the Internet at
http://pubs.acs.org. Spectroscopic data, theoretical calculations, X-ray crystallography data and a CIF
file for 4a.
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Acknowledgement. This study is partly supported by JST ERATO (JPMJER1301), JST PRESTO
(JPMJPR16N8), JST CREST (JPMJCR14L5) and KAKENHI (17H01033, 17K05772). We thank Dr.
M. Oinuma and Dr. S. Takahashi for the synthesis of precursors. A part of the results was computed at
the computer center of Kyoto University. We were granted access to the X-ray diffraction instruments
in SPring-8 BL38B1 beamline (no. 2017B1301).
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