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Titel: From Open-shell Singlet Diradicaloid to Closed-shell Global Anti-

aromatic Macrocycles

Autoren: Jishan Wu, Guangwu Li, Tullimilli Y. Gopalakrishna, Hoa

Phan, Tun Seng Tun Seng Herng, and Jun Ding

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Zitierweise: Angew. Chem. Int. Ed. 10.1002/anie.201803949

Angew. Chem. 10.1002/ange.201803949

Link zur VoR: http://dx.doi.org/10.1002/anie.201803949

http://dx.doi.org/10.1002/ange.201803949
Angewandte Chemie 10.1002/ange.201803949

COMMUNICATION
From Open-shell Singlet Diradicaloid to Closed-shell Global Anti-aromatic
Macrocycles
Guangwu Li,[a] Tullimilli Y. Gopalakrishna,[a] Hoa Phan,[a] Tun Seng Herng,[b] Jun Ding,[b] and Jishan
Wu*[a]
Abstract: A dithieno[a,h]-s-indacene (DTI) based diradicaloid of the thiophene ring can be easily brominated (i.e., DTI-2Br in
DTI-2Br was synthesized and its open-shell singlet diradical Scheme 1) and the angle between the terminal C-Br bonds is
character was validated by magnetic measurements. On the other nearly 105o (by calculation and also single-crystal structure, vide
infra), which will facilitate formation of macrocycles by Yamamoto

hand, its macrocyclic trimer DTI-MC3 and tetramer DTI-MC4
turned out to be closed-shell compounds with global anti-
aromaticity, which was supported by X-ray crystallographic
analysis and NMR spectra, assisted by ACID and 2D-NICS
calculations. Such change can be explained by a subtle balance
between two types of anti-ferromagnetic spin-spin coupling along
the π-conjugated macrocycles. The dications of DTI-MC3 and
DTI-MC4 turned out to be open-shell singlet diradical dications,
with a singlet-triplet energy gap of -2.90 and -2.60 kcal/mol,
respectively. At the same time, they are both global aromatic. Our
studies demonstrate that intramolecular spin-spin interactions
play important roles on electronic properties of π-conjugated
macrocycles.
Accepted Manuscript
coupling reaction. Accordingly, the diradicaloid monomer DTI-2Br
and its macrocyclic trimer DTI-MC3 and tetramer DTI-MC4
(Figure 1c) were synthesized. Bulky 4-tert-butyl-2,6-
dimethylphenyl group was used to block the most reactive sites to
obtain stable and soluble materials. The macrocycles can be
drawn in different resonance forms (Figure 1c), for example, an
open-shell hexa-/octa-radical form with all benzene and
thiophene rings being aromatic (form A), a closed-shell form in
which the spins are coupled in the same way to that in the
monomer and only three/four thiophene rings are aromatic (form
B), and a closed-shell form in which the spins are coupled through
the dithophene unit and only three/four benzenoid rings are
aromatic (form C). Thus, it will be interesting to know their ground-
state electronic structures and possible global (anti)aromaticity.
(a) J (b) Ar Ar Ar Ar

S S S S
In a simple two-site diradical model with two electrons in two
DTI
active orbitals, the exchange interaction (J) between the two spin J
J' (c)
centers is tunable by varying the interatomic distance (Figure 1a). Ar S S Ar

Intermediate electron correlation would result in open-shell singlet

ground state, and the diradical character index (y0) can be Ar Ar
controlled by the factors such as aromaticity, strain release and A
spatial distribution of the frontier molecular orbitals.[1] Our n-3 S S

particular interest now is the macrocyclic polyradicaloid made n Ar = But

S S
from the open-shell singlet diradicaloid, in which additional
electronic coupling (J’) between the diradicaloid units would lead Ar Ar
to π-conjugation along the macrocycle backbone (Figure 1a). Ar S S Ar Ar S S Ar

Such a topological change could give rise to possible appearance

of global aromaticity and polyradical character. Global aromaticity
Ar Ar
was normally observed in porphyrinoids,[2] but it was very rare for B
Ar
C
Ar

benzenoid polycyclic aromatic hydrocarbons because the large S S S S

resonance energy per π-electron for benzene ring drives the
electrons to predominantly localize at certain benzene rings rather
than delocalize to the whole framework.[3] However, global
aromaticity was recently attained in some non-alternant polycyclic
hydrocarbons[4] and macrocyclic polyradicaloids.[5] Our studies
also demonstrated that the polyradical character was
fundamentally determined by intramolecular spin-spin exchange
interactions.[5,6]
The design and synthesis of π-conjugated macrocycles from a
stable diradicaloid is challenging. Herein, we chose a
dithieno[a,h]-s-indacene (DTI) diradicaloid (Figure 1b) as the
building block based on the following considerations: (a) the
molecule recovers one aromatic benzene ring and one aromatic
thiophene ring in the diradical form, implying its potential open-
shell diradical character in the ground state similar to its
isoelectronic structure indeno[2,1-b]fluorene;[7] (b) the α-position
[a] Dr. G. Li, Dr. T. Y. Gopalakrishna, Dr. H. Phan, Prof. J. Wu
Department of Chemistry, National University of Singapore
3 Science Drive 3, 117543, Singapore
E-mail: chmwuj@nus.edu.sg
[b] Dr. T. S. Herng, Prof. J. Ding
Department of Materials Science and Engineering, National
University of Singapore, 119260, Singapore
Supporting information for this article is given via a link at the end of
the document.
n n
S S S S
DTI-MC3 (n=1)
Ar Ar DTI-MC4 (n=2) Ar Ar
Figure 1. (a) Schematic presentation on the change of the spin-spin exchange
interaction from the open-shell singlet diradicaloid to π-conjugated macrocyclic
polyradicaloids; (b) representative resonance forms of DTI; (c) representative
resonance forms (A-C) of macrocyclic DTI-MCn (n=3,4). The aromatic
thiophene and benzene rings are shaded in blue colour.
The synthesis commenced with Suzuki coupling reaction
between dimethyl 4,6-dibromobenzene-1,3-dioate (1) and
4,4,5,5-tetramethyl-2-(thiophen-3-yl)-1,3,2-dioxaborolane to give
the dimethyl 4,6-di(thiophen-3-yl)benzene-1,3-dioate (2) in 84%
yield (Scheme 1). Subsequent saponification followed by
conversion to the acid chloride and intramolecular Friedel−Crafts
acylation afforded the DTI dione 3 in 73% yield. Nucleophilic
addition of the two carbonyl groups in 3 by aryl lithium generated
the diol 4 in 54% yield. Interestingly, the diol sample isolated
turned out to be the syn diastereomer, which was confirmed by
NMR spectrum and the X-ray structure of its derivative 6 (inset in
Scheme 1). This stereo selectivity could be due to the large
electro-static repulsion when the second molecule of aryl lithium
adds to the carbonyl group of the mono-addition adduct from the
opposite side of the backbone to the OLi group initially formed,
similar to the reaction of 1,4-benzoquinone with aryl lithium
reagent.[8] The alcohol groups were then protected by methyl

This article is protected by copyright. All rights reserved. 1

Angewandte Chemie 10.1002/ange.201803949

COMMUNICATION
group with iodomethane to provide compound 5 in 83% yield. measurement revealed a singlet ground state and fitting of the
Bromination of 5 with N-bromosuccinimide or Br2 gave data by the Bleaney–Bowers equation[11] gave a singlet–triplet
complicated mixture. Alternatively, treatment with two equivalent energy gap (ES-T) of -3.6 kcal/mol (Figure S3). In addition, the
n-butyl lithium followed by addition of carbon tetrabromide gave aromatic protons on the backbone of DTI-2Br all appeared at high
the desired dibromide 6, and its syn stereo-structure was field (chemical shift  = 5.16, 6.34 and 6.00 ppm for protons a, b
confirmed by X-ray crystallographic analysis. The monomer DTI- and c, respectively, see labelling in Scheme 1) in its 1H NMR
2Br was then synthesized by chemical reduction of 6 with spectrum (193 K), in consistent with its anti-aromatic character.
SnCl2/HCl (sat.) in dichloromethane (DCM). However, the yield At the same time, the substituents are also partially shielded
was quite low (11%) and thus the intermediate 6 was chosen for (Figure S39).
the synthesis of macrocycles. Yamamoto coupling of 6 with
(a) (b) (c) 2 1.39 c
Ni(COD)2 in THF generated the macrocycles 7a/7b containing 1. 44
9 1.4 0 9 1.451
b

1.3
40

1.445
1 .73

1.447
1.73
4
a
three/four repeat units in 14% and 8% yield, respectively. 7

99
1.
S 0 1.43 S

0
1.4
1. 43 5

2
1.740
1 .3

1.737
1.4
88

21
92
Reduction of 7a/7b with SnCl2 in DCM gave the final products 1 .3

1.4
8
41
1.7 8 3

16
1. 37

1.

Accepted Manuscript
4

DTI-MC3 and DTI-MC4 in good yields. The obtained DTI-2Br, 1

6 S .79 77 S
(d) (e) (f) 75 a

1.
DTI-MC3 and DTI-MC4 all exhibited very good stability under
1 1 .7
1.

77
1.347

0
1. 427
1.356

1. 427
c

1.44
1.366

44
b

1.499
1.47

1 .4
ambient air and light conditions, with a half-life time of more than

1
1.
99 29 1.345 1 .349 44 1. 3
1 .3 1 .44 1.4 5 7 6
0 21
1 .4

1.373
one month as monitored by electronic absorption spectroscopy.

1 .377

1.375

1.404
84 1 . 83 1 .3 1.4
1.4 44 1 .3 81 85
2 23
1 .4

6 1.446
1 .36

1.451
O O

66
1 .46 6
O O O O 1 .441

1.3
1.732

1 .3 3

1.76
49
a MeO OMe b c

1 .3
MeO OMe S 43
9

1
1 .7 8 1 . 1.
42 S
84% 71% for S S 54% 4 3 86

1.3 1.776
1.7
1 .4
S S

53
three steps

93
Br Br 35

1.3
1. 436
2 3

68

1.3
1 .3

25
1 1 .4

1.766
1.3
54 73
0

2
.3 9

1.4
S1

47
1 5
1.45 S

1.

1 .425

1.429

23
.759
Ar MeO

1.3
Ar HO Ar MeO MeO Ar 1. 1.759

2
3

38
41
HO Ar MeO Ar 1 .477
94
51 .485

1.
9
d e f 1 .3

S S 83% S S 76% S S

4 5 Br 6 Br Figure 2. Top view (a, d) and side view (b, e) of the X-ray crystallographic
X-ray of 6
structure of DTI-2Br and DTI-MC3, the aryl substituents and hydrogen atoms
Ar S S OMe
MeO Ar Ar = But were omitted for clearance. (c, f) Selected bond lengths (Å) of the backbones.

Ar OMe
MeO Ar
h DTI-MC3 (n=1), 70%
DTI-MC4 (n=2), 64%
S S
n
S S
Ar OMe
7a (n=1), 14%
OMe Ar 7b (n=2), 8%
Scheme 1. Synthetic scheme of DTI-2Br, DTI-MC3 and DTI-MC4. Reagents
and conditions: (a) 4,4,5,5-tetramethyl-2-(thiophen-3-yl)-1,3,2-dioxaborolane,
Pd2(dba)3, K2CO3, THF, H2O, 90 oC; (b) i) NaOH, H2O, ethanol, 80 oC; ii) oxalyl
chloride, CH2Cl2, rt; iii) aluminum chloride, CH2Cl2, rt; (c) 5-tert-butyl-1,3-
dimethylphenyllithium, THF, -78 oC; (d) NaH, MeI, DMF, rt; (e) n-BuLi, CBr4,
THF, -78 oC→rt; (f) Ni(COD)2, THF, 65 oC; (g) SnCl2, HCl, CH2Cl2, rt; (h) SnCl2,
CH2Cl2, rt.
Single crystals suitable for X-ray crystallographic analysis
were obtained for DTI-2Br and DTI-MC3 by slow solvent diffusion
method.[9] DTI-2Br has a rigid backbone which is slightly deviated
from planarity (Figure 2a-b) and the aryl substituent showed a
large torsional angle (ca. 67o) with the mean plane of the
backbone. The bond a (1.445/1.447 Å) in the central six-
membered ring is much longer than that of typical C(sp2)-C(sp2)
double bond in benzene (1.39 Å), and there is also large bong
length alternation between bonds b (1.399/1.402Å) and c
(1.451/1.449 Å) in the cyclopenta- rings (Figure 2c), indicating
that the molecule still remains a major s-indacene sub-structure
after annulation with two aromatic thiophene rings. Anisotropy of
the induced current-density (ACID) calculations[10] clearly reveal a
counter-clockwise ring current flow along the central anti-aromatic
s-indacene moiety with little electron delocalization onto the
terminal thienyl units (Figure S8 in the Supporting Information
(SI)), further supporting this hypothesis. DTI-2Br exhibited
broadened 1H NMR spectrum in CD2Cl2 at room temperature
while decreasing the temperature eventually led to sharp peaks
at 193 K (Figure S1), indicating that DTI-2Br has open-shell
singlet diradical character and the NMR broadening is due to the
thermal population of triplet species at higher temperatures.
Indeed, our calculations (UCAM-B3LYP/6-31G(d,p)) predict that
DTI-2Br has a diradical character (y0) of 30%. DTI-2Br in the solid
state displayed a broad one-line ESR spectrum with ɡe = 2.0035
and the intensity decreased as the temperature was lowered
(Figure S2). The temperature-dependent magnetic susceptibility
measurements of DTI-2Br in powder form determined by
superconducting quantum interference device (SQUID)
Single-crystal structure of DTI-MC3 revealed a bowl-shaped
conformation and the distance between the mean planes of the
g 11%
outer-most and inner-most rims is about 1.649 Å (Figure 2c-d),
Ar Ar
a
indicating a large strain. The bond a (1.356/1.353/1.393 Å) linking
S S the DTI units is obviously shorter than that of a typical C(sp2)-
Br b
c
DTI-2Br Br C(sp2) single bond (1.45 Å), and the bonds b (1.349/1.345 Å) and
c (1.347/1.366 Å) are close to that in a typical olefin (1.33-1.35 Å),
all suggesting formation of a quinoidal dithiophene structure as
shown in form C in Figure 1c. That means, the anti-ferromagnetic
(AFM) spin-spin coupling in the macrocycles now prefers to the
form C rather than the form B, which is reasonable considering
that the three aromatic benzene rings in form C gain more
resonance energy than the three thiophene rings in form B. Single
crystals of DTI-MC4 quickly collapsed during the measurement
and thus its geometry was optimized by density functional theory
(DFT) calculations (B3LYP/6-31G(d,p)), which gave a nearly
planar backbone (Figure S7). Bond length analysis predicted a
similar double bond linkage between the DTI units, again
indicating that the form C in Figure 1c makes a major contribution.
Different from the monomer DTI-2Br, macrocycles DTI-MC3
and DTI-MC4 showed sharp 1H NMR spectra in CDCl3 and there
was almost no change with increasing or decreasing temperature,
indicating that that they both have closed-shell ground state. As
shown in Figure 3, protons a at the outer rim of the macrocyclic
backbone of DTI-MC3 appeared at high field (5.3 ppm), while
protons b and c on the inner rim became highly de-shielded ( =
11.35 and 11.21 ppm, respectively), indicating that the backbone
is globally anti-aromatic. Indeed, a 36-πe conjugation pathway
can be drawn (Figure S13), and the rigid geometry further
enforces the anti-aromatic character. The aromatic protons d/d’
on the substituents split into two sets of singlet ( = 7.05 and 6.83
ppm) due to the bowl-shaped geometry. DTI-MC4 with a 48-πe
conjugation pathway (Figure S14) exhibited similar feature,
except that the protons b/c ( = 10.10 and 10.12 ppm, respectively)
are less de-shielded (Figure 3), implying a weaker anti-aromatic
character. There was no spitting for protons d/d’ due to its planar
backbone. The change from open-shell singlet ground state for
the monomer to the closed-shell anti-aromatic macrocycles
implies that the AFM coupling (bonding) between the spins is
more efficient through the dithiophene spacer (loss of two
aromatic thiophene ring) than through the meta-benzenoid spacer
(loss of one aromatic benzene ring and one aromatic thiophene
ring).
2

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Angewandte Chemie 10.1002/ange.201803949

COMMUNICATION
DTI-MC3 * Ar Ar exhibits magnetic shielding (positive values) (Figure 4e,g), but
b S S DTI-MC3 displays stronger shielding/de-shielding effect, which
c d'd a S
n
S can well explain the observed chemical shifts in 1H NMR.
Ar Ar
d
a c Ar = Compound DTI-2Br in DCM shows intense absorption band
* Ar b
d'
Ar with maximum (max) at 654 nm (Figure 5a), which can be
DTI-MC32+
S S assigned to the HOMO-1→LUMO (25%)/HOMO→LUMO (76%)
d d'
a cb
S S
n=0,1
electronic transitions (max = 648 nm, oscillator strength f = 0.6672)
Ar Ar according to time-dependent (TD) DFT calculations (see SI). In
* d,d' addition, a very weak and broad band was found in the region of
DTI-MC4
b 800-1600 nm (inset in Figure 5a), which can be correlated to the
a
c almost forbidden HOMO-1→LUMO (74%)/HOMO→LUMO (26%)
transitions (max = 1064 nm, f = 0.0107). Such weak absorption

DTI-MC42+
d,d' * was frequently observed for anti-aromatic compounds.[14] DTI-
a c
12 10 8 6 4 -2 -4
Chemical Shift (ppm)
1
Figure 3. H NMR spectra of DTI-MC3, DTI-MC4 (measured at 298 K) and their
dications (measured at 213 K), the peaks labeled as * indicate residue solvents.
Both ACID plot and nucleus independent chemical shift
(NICS)[12] calculations were conducted to better understand the
global anti-aromaticity. The ACID plots of the backbone of DTI-
MC3 (Figure 4a) and DTI-MC4 (Figure 4c) clearly show counter-
clockwise paratropic ring current flow along the macrocyclic
backbone, and electron delocalization pathway goes through the
inner rim and outer rim alternatingly, but very less onto the sulfur
atoms (see more magnified ACID plots viewed from different
angles in SI and Figures S13-S14 for the ChemDraw drawing of
the conjugation pathway). The NICS(0) value at the geometry
center was calculated to be +7.02 ppm for DTI-MC3 and +4.88
pm for DTI-MC4, in consistent with their anti-aromatic character
and the observed trend. In addition, the iso-chemical shielding
surface (ICSS)[13] calculations were carried out to analyze two-
dimensional (2D) ICSS values depending on various planes. In
both cases, the inner cavity area shows magnetic de-shielding
(negative values) while the outside area of the macrocycle
Accepted Manuscript
MC3 and DTI-MC4 exhibit intense absorption band with max at
b 558 and 650 nm, respectively, with a long tail to the near-infrared
(NIR) region (Figure 5a) which can be correlated to partially
-6 -8 forbidden transitions for these anti-aromatic macrocycles (see
more details about the TD DFT calculations in SI).
Compound DTI-2Br showed one reversible oxidation wave
with E1/2ox at 0.31 V (vs Fc+/Fc) and one reversible reduction wave
with E1/2red at -1.20 V in its cyclic voltammogram (Figure 5b), and
this amphoteric redox behavior is common for open-shell
diradicaloids. DTI-MC3 exhibited two reversible oxidation waves
(E1/2ox at -0.01 and 0.22 V) and one overlapped reduction wave
(E1/2red at -1.22 V), while DTI-MC4 displayed four reversible
oxidation waves (E1/2ox at 0.05, -0.17, 0.55 and 0.70 V) and three
reduction waves (E1/2red at -1.12, -1.60 and -1.69 V) (Figure 5b).
Therefore, extension of π-conjugation led to more accessible
redox states and decrease of the electrochemical energy gap
(1.51 eV→1.22 eV→1.17 eV). Chemical titration of DTI-MC3 by
oxidant NO•SbF6 in DCM gave its radical cation (RC) and dication
(DC), both showing long-wavelength absorption in the NIR region
(max = 2180 and 2340 nm, respectively, Figure 5c) and the
observed spectra are in agreement with the TD DFT calculations
(see SI). For DTI-MC4, the titration did not stop at the RC stage,
and thus only the spectrum of the DC was recorded (max = 2445
nm). Pure dications of DTI-MC3 and DTI-MC4 were isolated, and

Figure 4. ACID plots of the backbone molecules of (a) DTI-MC3, (b) DTI-MC32+; (c) DTI-MC4 and (d) DTI-MC42+. The magnetic field is perpendicular to the XY
plane and points out through the paper. The blue and red arrows indicate the clockwise (diamagnetic) and counter-clockwise (paramagnetic) current flow,
respectively. 2D-ICSS maps of the backbone molecules of (e) DTI-MC3, (f) DTI-MC32+; (g) DTI-MC4 and (h) DTI-MC42+. The top and bottom images are mapped
at XY and XZ plane, respectively.

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Angewandte Chemie 10.1002/ange.201803949

COMMUNICATION
interestingly, their 1H NMR spectra were both broadened at room global aromatic. These new macrocycles represent a rare type of
temperature and became sharper with decreasing temperature non-porphyrinoid global (anti)aromatic system. Our study
(Figures S4-S5), indicating open-shell singlet ground state. highlights the important role of intramolecular spin-spin coupling
Variable temperature ESR measurements of the dications in DCM
on the electronic properties of π-conjugated macrocycles.
showed a featureless broad signal (ɡe = 2.0034 for both) and the
intensity decreased as the temperature was lowered (Figure S6),
indicating that they can be regarded as diradical dications. Fitting Acknowledgement
of the data by the Bleaney–Bowers equation gave a ES-T value
of -2.90 and -2.60 kcal/mol, respectively. The 1H NMR spectra of
the dication of DTI-MC3/DTI-MC4 recorded at 213 K clearly We acknowledge financial support from the MOE Tier 3
showed that the outer-rim protons a were de-shielded (7.76/10.79 programme (MOE2014-T3-1-004). We thank Dr. Tan Geok
ppm), while the inner-rim protons b (-3.48/-7.91 ppm) and c (- Kheng for her help on X-ray crystallographic analysis.
3.22/-7.29 ppm) were highly shielded (Figure 3), indicating a

global aromatic system and the larger macrocycle exhibited
stronger magnetic character. ACID plots showed clockwise
diatropic ring current flow for both dications, with the frontier π
electrons mainly delocalized along the inner rim (Figures 4b,d).
The NICS(0) values now become negative (-12.48/-12.55 pm),
and the 2D-ICSS maps further confirm an inverse of aromaticity
of the macrocycles after losing two π electrons (Figures 4f,h).
Indeed, a 34/46-πe conjugation pathway can be drawn for the
dication of DTI-MC3/DTI-MC4 (Figures S13-S14), satisfying
[4n+2] Hückel aromaticity rule. In addition, both dications can
recover one aromatic benzene ring and one aromatic thiophene
ring in their diradical forms (Figures S13-S14), which could serve
as the major driving force to become diradical.
(a)
DTI-MC3
654
Accepted Manuscript
Keywords: macrocycle • diradicaloid • polyradicaloid •
aromaticity • global aromaticity
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DTI-2Br

15
DTI-MC4 DTI-MC3 [3] (a) E. Clar, Aromatic Sextet, John Wiley & Sons Ltd, 1972. (b) J. Aihara, J.
DTI-2Br DTI-MC4
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+
0.31

Shimizu, E. Botek, B. Champagne, D. Shiomi, K. Sato, T. Takui, K.

650

12 +
-1.20

DTI-2Br
)
1
-
0.3
Matsumoto, H. Kurata, T. Kubo, J. Am. Chem. Soc. 2010, 132, 11021. (d)
Current

m
558

-0.01

c
1 9
)
1
Z. Sun, S. Lee, K. Park, X. Zhu, W. Zhang, B. Zheng, P. Hu, Z. Zeng, S.
- -
+
963

m
M 0.2
+
-1.22

c
Das, Y. Li, C. Chi, R. Li, K. Huang, J. Ding, D. Kim, J. Wu, J. Am. Chem.
0.22

1
-
4 M
0
1192

1
(
4
0
1 + Soc. 2013, 135, 18229. (e) J. C. Buttrick, B.T. King, Chem. Soc. Rev. 2017,
1443

(
6


0.1 +


46, 7.
0.05

0.70

+
+
+ + [4] (a) E. Steiner, P. W. Fowler, L. W. Jenneskens, Angew. Chem. Int. Ed. 2001,
0.55
-1.69

3
0.17

0.0
+
40, 362. (b) H. Miyoshi, S. Nobusue, A. Shimizu, Y. Tobe, Chem. Soc. Rev.
-1.12

900 1200 1500 1800

-1.60

Wavelength (nm) +
2015, 44, 6560. (c) Q. Wang, T. Y. Gopalakrishna, H. Phan, T. S. Herng, S.
0

300 600 900 1200 1500 1800 -2.0 -1.5 -1.0 -0.5 0.0 0.5
Dong, J. Ding, C. Chi, Angew. Chem. Int. Ed. 2017, 55, 11415. (d) C. Liu,
Wavelength (nm) Potential (V) vs. Fc+/Fc M. E. Sandoval-Salinas, Y. Hong, T. Y. Gopalakrishna, H. Phan, N. Aratani,
10
(c) DTI-MC3 (d) T. S. Herng, J. Ding, H. Yamada, D. Kim, D. Casanova, J. Wu, Chem 2018,
558

DTI-MC4
650

DTI-MC3 RC 12 DTI-MC4 DC
DTI-MC3 DC
accepted.
8
10
[5] (a) S. Das, T. S. Herng, J. L. Zafra, P. M. Burrezo, M. Kitano, M. Ishida, T.Y.
) Gopalakrishna, P. Hu, A. Osuka, J. Casado, J. Ding, D. Casanova, J. Wu.
) 1
1 -
- m J. Am. Chem. Soc. 2016, 138, 7782. (b) X. Lu, S. Lee, Y. Hong, H. Phan, T.
m 6 c 8
c 1
702

-
1
M Y. Gopalakrishna, T. S. Herng, T. Tanaka, M. E. Sandoval-Salinas, W. Zeng,
1098

-
M
853

4
0
4
0 1 6 J. Ding, D. Casanova, A. Osuka, D. Kim, J. Wu. J. Am. Chem. Soc. 2017,
1
( 4
(
139, 13173.



1006

4
[6] P. Hu, S. Lee, T. S. Herng, N. Aratani, T. P. Gonçalves, Q. Qi, X. Shi, H.
2445
2180

2
2 x x x x
Yamada, K.-W. Huang, J. Ding, D. Kim, J. Wu, J. Am. Chem. Soc. 2016, 138,
2340

0
0
500 1000 1500 2000 2500 3000
Wavelength (nm)
Figure 5. UV-visible-NIR absorption specta (a) and cyclic voltammograms (b)
of DTI-2Br, DTI-MC3 and DTI-MC4; (c) and (d) asborption spectra of the radcial
cation (RC) and dictaion of DTI-MC3 and DTI-MC4 obtained by titration with
NO•SbF6, in comparison with the spectra of their nertal compounds. The sign
“x“ in (d) indicates that the overtone peaks from solvent were cut for clarity.
In summary, transformation from an open-shell singlet
diradicaloid (DTI-2Br) to macrocycles DTI-MC3 and DTI-MC4 led
to closed-shell global anti-aromatic systems with [4n] π electrons.
Such change is due to a subtle balance between two types of
AFM coupling interactions between the spins along the
macrocycle backbone. Two-electron oxidation resulted in open-
shell diradical dications containing [4n-2] π electrons which are
x 1065.
x xx x x [7] A. Shimizu, R. Kishi, M. Nakano, D. Shiomi, K. Sato, T. Takui, I. Hisaki, M.
500 1000 1500 2000 2500 3000 Miyata, Y. Tobe, Angew. Chem. Int. Ed. 2013, 52, 6076.
Wavelength (nm) [8] F. Alonso, M. Yus, Tetrahedron 1991, 47, 7471.
[9] Crystallographic data for compounds 6 (CCDC no.: 1834313), DTI-2Br
(CCDC no.: 1834314) and DTI-MC3 (CCDC no.: 1834315) are deposited in the
Cambridge Crystallographic Data Center (CCDC).
[10] D. Geuenich, K. Hess, F. Köhler, R. Herges, Chem. Rev. 2005, 105, 3758.
[11] B. Bleaney, K. D. Bowers, Proc. R. Soc. London Ser. A 1952, 214, 451.
[12] Z. Chen, C. S. Wannere, C. Corminboeuf, R. Puchta, P. v. R. Schleyer,
Chem. Rev. 2005, 105, 3842.
[13] (a) S. Klod, E. Kleinpeter, J. Chem. Soc., Perkin Trans. 2 2001, 1893. (b)
T. Lu, F. Chen, J. Comput. Chem. 2012, 33, 580.
[14] J.-Y. Shin, K. S. Kim, M.-C. Yoon, J. M. Lim, Z. S. Yoon, A. Osuka, D.
Kim, Chem. Soc. Rev. 2010, 39, 2751.

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Angewandte Chemie 10.1002/ange.201803949

COMMUNICATION
COMMUNICATION
Global (anti)aromatic macrocycles! G. Li, T. Y. Gopalakrishna, H. Phan, T.
Macrocyclization of open-shell S. Herng, J. Ding, and J. Wu*
diradicaloids led to closed-shell global
anti-aromatic macrocycles, which Page No. – Page No.
could become global aromatic
From Open-shell Singlet Diradicaloid
diradical dications upon two-electron
to Closed-shell Global Anti-aromatic
oxidation. The subtle balance of
Macrocycles
intramolecular spin-spin interaction
plays the key role on the ground-state

Accepted Manuscript
electronic properties of these
macrocycles.

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