Supporting Information for

Molecular face-rotating cube with emergent chiral and

fluorescence properties
Hang Qu1 , Yu Wang1* , Zhihao Li1 , Xinchang Wang1 , Hongxun Fang1 , Zhongqun Tian1 , and
Xiaoyu Cao1*
1
State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM and College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen 361005, China.
*
e-mail: roywangyu@gmail.com,xcao@xmu.edu.cn

Contents
1 Supplementary Figures S2

2 Supplementary Tables S15

3 Supplementary Methods S16

S1
1 Supplementary Figures

O 1. Zn TiCl4
2. pyridine

THF
0 ºC to reflux, 15 h
yield: 90%
TPE

H H
Br Br O O

1. n-BuLi
Br2, FeCl3 2. DMF
CHCl3, r.t. Et2O
yield: 94% 0 ºC to r.t.
yield: 72%
Br Br O O
H H
TBPE ETTBA

Figure S1: Representative procedure for the synthesis of the facial building block ETTBA.

S2
 5+
681.77

Simulated

4+ 851.0 851.5 852.0 852.5 853.0 853.5 854.0

851.96

(6M)-1
Experimental

851.0 851.5 852.0 852.5 853.0 853.5 854.0

m/z

3+
1135.61 2+
1702.90

600 800 1000 1200 1400 1600 1800

5+
681.77

Simulated

4+
851.0 851.5 852.0 852.5 853.0 853.5 854.0
851.96

(2P4M)-2
Experimental

851.0 851.5 852.0 852.5 853.0 853.5 854.0

m/z

3+
2+
1135.27 1702.90

600 800 1000 1200 1400 1600 1800

m/z

Figure S2: ESI-MS spectra of (6M )-1 (top spectrum) and (2P 4M )-2 (bottom spectrum).
The inset images show the simulated (top) and experimental (bottom) isotopic distributions of
[C228 H217 N32 ]4+ and [C228 H217 N32 ]4+ species for (6M )-1 and (2P 4M )-2, respectively.

S3
 mv
300
Ch1 300 nm

16.730
(6M)-1
Peak No. R. Time Area Ratio
1 13.224 73670 0.222
2 16.730 12534815 37.708
3 19.250 4076251 12.262

24.434
(6P)-1
4 24.434 12432496 37.398
5 28.856 4125601 12.410
200 Total 33242833 100
2000

0.886
(2P4M)-2
R. Time Area
1500
0.886 33268585

19.250

(4P2M)-2
13.224 ETTBA

28.856
100 1000

500

0
0 0.5 1 1.5
0

0 10 20 30 40 50 60 min

Figure S3: The full chiral HPLC spectrum reveals that the synthetic product contains only 0.2%
unreacted ETTBA and four cage isomers (6M )-1, (2P 4M )-2, (6P )-1 and (4P 2M )-2 in a 3:1:3:1
ratio. As a comparison, a parallel HPLC analysis was carried out without using the column, and
the result is shown in the inset.The overall peak areas of the fractions passed through the column
(3.324 × 107 ) matches well with the peak area in the spectrum obtained without passing through
the column (3.326 × 107 ), indicating that all the fractions were shown in the HPLC spectrum.

S4
 CHCl3 residue

TMS
H 2O

protons on TPE faces protons on TREN vertices

and imine bonds
Toluene

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
f1 (ppm)

Figure S4: 600 MHz 1 H NMR spectrum of (6P )-1.

a b

7º
70º 61º

60º 20º 2º

60º 60º 73º

Figure S5: Crystal structures of (6M )-1 (a) and (2P 4M )-2 (b) to illustrate the phenyl
configurations on vertex (yellow line), the dihedral angles between phenyl ring and vinyl bond
(red line) and the dihedral angles between the adjacent imine bond and phenyl ring (cyan line).

S5
 (6P)-1 (6P)-1 (6P)-1

(4P2M)-2 (4P2M)-2 (4P2M)-2

Figure S6: Single crystal structures and the corresponding cartoons for (6P )-1 and (4P 2M )-2.

S6
 a b
(6M)-1 (6M)-1
Intensity / a.u.

Intensity / a.u.
(6P)-1
(2P4M)-2

(2P4M)-2
(4P2M)-2 (4P2M)-2

(6P)-1
15 20 25 30 15 20 25 30
Retention Time / min Retention Time / min

Figure S7: Chiral HPLC spectra recorded by the UV-vis detection (a) and the online optical
rotation detection (b) reveal four fractions corresponding to (6M )-1, (2P 4M )-2, (6P )-1 and
(4P 2M )-2 in a 3:1:3:1 ratio.

a b
(6M)-1 (2P4M)-2
0.5
[θ] / 106 deg cm2 dmol-1

[θ] / 106 deg cm2 dmol-1

0 0

-1 -0.5
(6P)-1 (4P2M)-2
250 300 350 400 450 250 300 350 400 450
Wavelength / nm Wavelength / nm

Figure S8: Experimental and (ZINDO/S)-predicted (the insert) CD spectra of (6M )-1 (red)
and (6P )-1 (purple) (a), (2P 4M )-2 (blue) and (4P 2M )-2 (green) (b).

S7
 a b
2 24 h
[θ] / 106 deg cm2 dmol-1

24 h
0h

Intensity / a.u.
0h
1

-1

-2

250 300 350 400 450 15 20 25 30

Wavelength / nm Retention Time / min

Figure S9: CD (a) and HPLC (b) spectra of (6P )-1 before and after heated in the chloroform
solution at 60◦ C for 24 hours.

4000
Tol
CHCl3
3000 Et2O
Intensity / a.u.

EA
2000 CH3CN

1000

0
400 450 500 550 600 650
Wavelength / nm

Figure S10: Fluorescence spectra of 1 in different solvent at the concentration of 10 µM (excited

at 340 nm).

S8
 B flipping
4 rings
42.5º 137.5º
A
Relative energy (kJ mol-1)

500 (M)-TPE (P)-TPE

pathway in (B)
400 pathway in (C) C
pathway in (D) flipping
300 4 rings
200
100
(6M)-1 (5M1P)
0 D
flipping
10 50 90 130 170 24 rings
Dihedral angle (degree)

(6M)-1 (6P)-1

Figure S11: DFTB+ calculations of the phenyl flipping in TPE monomer and (6M )-1.
(A), Potential energy surfaces of the different pathways to flip the phenyl rings in TPE and (6M )-
1. (B), Pathway to synchronously flip the four phenyl rings of lowest energy structure of (M )-TPE
to its mirror-image (P )-TPE by increasing the CP h -CP h -C=C dihedral angle from 42.5◦ to 137.5◦ .
(C), Pathway to synchronously flip the four phenyl rings on the top face of (6M )-1 with the TPE
units on other faces fixed. (D), Pathway to synchronously flip the 24 phenyl rings in (6M )-1 to
its mirror-image (6P )-1.

S9
 a b

0.4º 1.6º

50º 40º
45º 35º

c d

1.5º 4.6º

65º 70º 90º

85º

Figure S12: DFTB+ calculated structures of the T -symmetric (6M )-1 with the different CP h -
CP h -C=C dihedral angles. The optimized structure without any restriction of atoms (a) contains
two kinds of CP h -CP h -C=C dihedral angles, i.e., 45◦ and 50◦ . The structures in (b–d) were
constructed based on the optimized structure in (a), by rotating all the phenyl groups in -10◦ (b),
+20◦ (c) and +40◦ (d). And the the vertex configurations of (b–d) were further optimized with
the fixed CP h -CP h -C=C dihedral angles. The yellow lines show the CP h -CP h -C=C dihedral angles
in each structures. The cyan lines show the dihedral angles between the imine bonds and the
attached phenyl groups. These four representative structures are selected to illustrate that every
imine bond follows the rotation of its attached phenyl ring and keep in the same plane of the
phenyl ring during the flipping of TPE faces.

S10
 C71
N10
C70

N9

C69
C54
C68 N8
C53
C48 C55
C49 C52
C67 C56
C50 C51
C47 C38 C58
C33 C46 C76
C45 C57
C59
C37
N4 C32
N12
C31 C39 C62
C30 C18 C75
C13 C17 C19 C40
C44
C60
C16 C41 C61 N11
C20 C72
C14 C43 C42 C74
N3 C12 C15 C73
C63 N7
C2 C21
C11 C9 C22
C1
C10 C23 C65
C8 C64
C3 C26 C34
C7 C25 C66
C24
C4 N6
C6 C36
C5 N5
C35

C27
N2

C28
N1
C29

Figure S13: ORTEP drawing of (6M )-1 (displacement ellipsoids for all non-H atoms at the 50%
probability level).

S11
 C66 C67
C65

N4
N3 C29
C32
C64 C31
C28
C43 N5 C30
C44
C42 C27 C7 C11 N11
C6 N10
C45 C12
C41
C5 C8 C10 C13
C39 C40

C46 C4 C14
C38 C47 C3 C9
C52 C2 C1
C57 C48
C21 C20
C51 C68
C50 C49 C19
C53 C22 C26
C56 C15
N6 C23 C18
C25
C69 C16
N2 C55 C54 C59 C70 C24 C33
C35 C17 N12
C76 C58
N1 C71 C34
C74 N9
C75 C63
N7
C72 C37
N8
C73 C61 C36
C62

Figure S14: ORTEP drawing of (6P )-1 (displacement ellipsoids for all non-H atoms at the 50%
probability level).

S12
 C34

N8

C33

C23 C31
C24 C32
C30
C25 C22
C18 N7
C19
C26 C20
C17
C21
C8
C15 C16
C57 C7 C2 C9
C1
C3 C10
N1 C37 N3 C6
C11
C4
C56 C14
C5 C12
C54 C35
C55 C36 N6
C13
C47 C46 C41 C51 C27
N2 C48 C40
C45 C39 C28
C52
C42
C49 C29
C44 C43 N4
C50 C38
N5
C53

Figure S15: ORTEP drawing of (2P 4M )-2 (displacement ellipsoids for all non-H atoms at the
50% probability level).

S13
 C57 C54
C51

N6 C56
C50 C53

N5 N7 N8

C55 C52
C47 C49
C24
C48 N4 C18 C36
C30 C23
C17 C37
C46 C35
C45 C19 C16 C25
C38 C22
N3 C29
C15
C43 C31 C20 C39
C34
C42 C28 C26 C21
C32 C27
C44 C33
C41
N2
C6
C5

C7
C4
C3
C8
C11 C10
C12 C1
C40
C9 C2

N1 C14
C13

Figure S16: ORTEP drawing of (4P 2M )-2 (displacement ellipsoids for all non-H atoms at the
50% probability level).

S14
2 Supplementary Tables

Table S1: Crystal parameters for the four FRCs

Compound (6M )-1 (2P 4M )-2 (6P )-1 (4P 2M )-2
Empirical formula C228 H216 N32 C228 H216 N32 C228 H216 N32 C228 H216 N32
Formula weight 3404.32 3404.32 3404.32 3404.32
Temperature/K 223.01(10) 150.00(10) 223.00(10) 150.00(10)
Crystal system trigonal hexagonal trigonal hexagonal
Space group R3 P64 22 R3 P62 22
a/Å 28.1211(9) 35.7068(6) 29.0242(9) 35.6733(20)
b/Å 28.1211(9) 35.7068(6) 29.0242(9) 35.6733(20)
c/Å 30.4311(13) 22.6261(4) 30.6505(11) 22.6222(16)
α/◦ 90 90 90 90
β/◦ 90 90 90 90
γ/◦ 120 120 120 120
Volume/Å3 20840.7(16) 24982.9(10) 22360.9(16) 24932(3)
Z 3 3 3 3
ρcalc g/cm3 0.814 0.679 0.758 0.680
µ/mm−1 0.377 0.314 0.351 0.315
F(000) 5424.0 5424.0 5424.0 5424.0
Crystal size/mm3 0.2×0.2×0.2 0.2×0.2×0.2 0.2×0.2×0.2 0.1×0.1×0.1
CuKα (λ = CuKα (λ = CuKα (λ = CuKα (λ =
Radiation
1.54184 Å) 1.54184 Å) 1.54184 Å) 1.54184 Å)
2Θ range for
6.85 to 130.074 6.924 to 142.232 10.59 to 142.348 6.93 to 122.336
data collection/◦
-32≤h≤33, -41≤h≤43, -26≤h≤35, -40≤h≤33,
Index ranges -33≤k≤29, -37≤k≤31, -35≤k≤33, -31≤k≤39,
-35≤l≤25 -27≤l≤26 -35≤l≤37 -25≤l≤25
Reflections collected 35455 99433 53848 73412
12455 [Rint = 15952 [Rint = 16778 [Rint = 12788 [Rint =
Independent reflections
0.0373,Rsigma =0.0460] 0.0737,Rsigma =0.0435] 0.0675,Rsigma =0.0663] 0.1669,Rsigma =0.1004]
Data/ restraints
12455/15/781 15952/0/587 16778/44/733 12788/0/587
/ parameters
Goodness-of-fit on F2 0.965 0.941 0.903 0.887
R1 = 0.0569, ωR2 R1 = 0.0548, ωR2 R1 = 0.0577, ωR2 R1 = 0.0597, ωR2
Final R indexes[I≥2σ(I)]
= 0.1529 = 0.1468 = 0.1463 = 0.1405
R1 = 0.0822, ωR2 R1 = 0.0797, ωR2 R1 = 0.1044, ωR2 R1 = 0.1179, ωR2
Final R indexes [all data]
= 0.1763 = 0.1676 = 0.1796 = 0.1731
Largest diff. peak /
0.27/-0.14 0.20/-0.21 0.25/-0.17 0.13/-0.19
hole / e Å−3
Flack parameter 2.4(3) 1.95(17) 2.0(3) 0.9(3)
CCDC# 1554496 1554462 1554480 1554495

S15
3 Supplementary Methods

Graph theory analysis of FRCs.

Six faces of a 1×1×1 cube centered on (0.5, 0.5, 0.5) can be described by their intercepts on x,
y, and z axials:

• Face 1 : {∞, ∞, 0}

• Face 2 : {∞, ∞, 1}

• Face 3 : {∞, 0, ∞}

• Face 4 : {∞, 1, ∞}

• Face 5 : {0, ∞, ∞}

• Face 6 : {1, ∞, ∞}

First, we only consider the patterns of the ethenyl groups. The orientations of the ethylene
groups on cube faces could be described by three vectors: i (1,0,0), j (0,1,0), and k (0,0,1).
Because the ethylene mark only has orientation but not directions, therefor the -i, -j, and -k
would considered the same as i, j, and k, respectively.
Cubes with different facial patterns can be described by a set M containing the ethylene vectors
on each faces from 1 to 6 : M = {i(j), i(j), i(k), i(k), j(k), j(k)}.
The numbers of i, j, and k in the set M are defined as n, m, and l, respectively. There are two
restrictions for n, m, and l: n+m+l = 6 and 0 ≤ n, m, l ≤ 4. Therefore, the possible values of the
matrix [n, m, l] are listed as follows:

[4,2,0], [4,0,2], [2,4,0], [2,0,4], [0,4,2], [0,2,4]

[4,1,1], [1,4,1], [1,1,4]
[n,m,l] = [3,3,0], [3,0,3], [0,3,3]
[3,2,1], [3,1,2], [2,1,3], [2,3,1], [1,3,2], [1,2,3]
[2,2,2]

We only need to analysis [4,2,0], [4,1,1], [3,3,0], [3,2,1] and [2,2,2] as five reprehensive cases.
The rest cases can be converted to the five reprehensive cases by changing the turns of n, m, and
l through the C 4 rotational operations along the i, j, or k vectors.
When the n, m, and l are settled, only three C 2 rotational operations along i, j, and k are
allowed to find the equivalent cubes with same [n,m,l], because they would not change the values
of n, m, and l. By contrast, the other symmetry operations, e.g., six C 2 rotational operations

S16
along (i + j), (i − j), (i + k), (i − k), (j + k) and (j − k) vectors, and four C 3 rotational operations
along (i + j + k), (i + j − k), (i − j + k) and (j + k − i) vectors, are not always allowed, because
they could change the values of n, m, and l.
Three C 2 rotational operations along i, j, and k can be expressed as three permutation groups
to the set M :
σ(C2 (i)) = (12)(34)
σ(C2 (j)) = (12)(56)
σ(C2 (k)) = (34)(56)

Using these three permutation groups, we are able to find the equivalent cubes for the five
reprehensive cases with [n,m,l] values of [4,2,0], [4,1,1], [3,3,0], [3,2,1] and [2,2,2] as follows:

[n,m,l] M Equivalent sets Chirality

[4,2,0] {i,i,i,i,j,j} None Achiral
[4,1,1] {i,i,i,i,k,j} {i,i,i,i,j,k} Achiral
[3,3,0] {i,j,i,i,j,j} {j,i,i,i,j,j} Achiral
[3,2,1] {i,i,k,i,j,j} {i,i,i,k,j,j} Achiral
[3,2,1] {i,j,i,i,j,k} {j,i,i,i,j,k}, {i,j,i,i,k,j}, {j,i,i,i,k,j} Achiral
[2,2,2] {i,i,k,k,j,j} {j,j,i,i,k,k} Achiral
[2,2,2] {i,j,i,k,k,j} {j,i,k,i,k,j}, {j,i,i,k,j,k}, {i,j,k,i,j,k} Chiral
[2,2,2] {i,j,i,k,j,k} {j,i,k,i,j,k}, {j,i,i,k,k,j}, {i,j,k,i,k,j} Chiral

Therefore, when we only consider the patterns of the ethylene groups, there are 8 different
patterned cubes, including six achiral cubes and a pair of chiral enantiomers.
Then, we introduce the rotational (P /M ) patterns onto the 8 cubes with different facial
orientational patterns. Since the rotational directionality of the P or M pattern would not change
upon the symmetry operations, this painting problem of (P /M ) patterns was similar to the classic
polyhedron coloring problem. Hence, we solve this problem by analyzing the symmetry elements
of the 8 cubes and the permutation groups of facial orientational patterns, as listed in the following
table.
Overall, there are 28 + 24 + 24 + 40 + 64 + 12 + 16 + 16 = 224 types of patterned cubes. Among
them, only four are achiral mesomers: {i&P , i&M , i&P , i&M , j&P , j&M }, {i&P , i&M , i&P ,
i&M , j&M , j&P }, {i&P , i&M , k&P , k&M , j&P , j&M } and {i&P , i&M , k&P , k&M , j&M ,
j&P }.

S17
 M Symmetry elements Permutation groups Types of painted cubes
E (1)(2)(3)(4)(5)(6)
C2 (i) (12)(34)(5)(6) (26 + 3 × 24 )
{i,i,i,i,j,j} = 28
C2 (j) (12)(3)(4)(56) 4
C2 (k) (1)(2)(34)(56)
E (1)(2)(3)(4)(5)(6)
C2 (i) (12)(34)(5)(6) (26 + 24 + 2 × 23 )
{i,i,i,i,k,j} = 24
C2 (j + k) (13)(24)(56) 4
C2 (j − k) (14)(23)(56)
E (1)(2)(3)(4)(5)(6)
C2 (k) (1)(2)(34)(56) (26 + 24 + 2 × 23 )
{i,j,i,i,j,j} = 24
C2 (i + j) (12)(35)(46) 4
C2 (i − j) (12)(36)(45)
E (1)(2)(3)(4)(5)(6) (26 + 24 )
{i,i,k,i,j,j} = 40
C2 (j) (12)(3)(4)(56) 2
{i,j,i,i,j,k} E (1)(2)(3)(4)(5)(6) 26 = 64
E (1)(2)(3)(4)(5)(6)
C2 (i) (12)(34)(5)(6)
C2 (j) (12)(3)(4)(56)
C2 (k) (1)(2)(34)(56) (26 + 3 × 24 + 8 × 22 )
{i,i,k,k,j,j} = 12
C3 (i + j + k), C32 (i + j + k) (135)(246), (153)(264) 12
C3 (i − j + k), C32 (i − j + k) (145)(236), (154)(263)
C3 (i + j − k), C32 (i − j + k) (235)(146), (253)(164)
C3 (j + k − i), C32 (i − j + k) (136)(245), (163)(254)
E (1)(2)(3)(4)(5)(6)
C2 (i − j) (12)(36)(45)
(26 + 3 × 23 + 2 × 22 )
{i,j,i,k,k,j} C2 (j + k) (13)(24)(56) = 16
6
C2 (i + k) (15)(34)(26)
C3 (i + j − k), C32 (i − j + k) (235)(146), (253)(164)
E (1)(2)(3)(4)(5)(6)
C2 (i + j) (12)(35)(46)
(26 + 3 × 23 + 2 × 22 )
{i,j,i,k,j,k} C2 (j + k) (13)(24)(56) = 16
6
C2 (i − k) (16)(34)(26)
C3 (i − j + k), C32 (i − j + k) (145)(236), (154)(263)

S18
Synthesis of ETTBA. ETTBA was synthesised from benzopheone within three steps as shown
in Fig. S1. The first two steps to form 1,1,2,2-tetrakis(4-bromophenyl)ethene (TBPE) are similar
to the reported procedures. In the third step, n-BuLi (15.6 mmol, 6.5 mL, 2.4 M in hexane) was
added to the ethyl ether solution of TBPE (2.0 g, 1.3 mmol) at −78◦ C under nitrogen. After
stirred for 2 h, the reaction mixture was allowed to warm up to 0◦ C for 30 min and was further
stirred for another 30 min at room temperature. The mixture was further cooled to −78◦ C, and
N,N-dimethylformamide(1.2 mL, 16.6 mmol) was added and stirred for 2 h. Then the reaction
solution was allowed to warm up to room temperature and stirred overnight. The reaction was
quenched by 2 M HCl aqueous solution (20 mL) and was further extracted by dichloromethane
(3×10 mL). The combined organic layers were dried over anhydrous sodium sulfate and evaporated
in vacuum, and the solid was purified by column chromatography with dichloromethane to give
ETTBA as yellow powder (yield 72%).
ETTBA. 1 H NMR (500 MHz, CDCl3 , ppm, δ): 9.94 (s, 4H), 7.68 (d, J = 8.1 Hz, 8H), 7.19 (d,
J = 8.1 Hz, 8H).13 C NMR (125 MHz, CDCl3 , δ): 191.47, 147.90, 142.19, 135.31, 131.77, 129.61.
HRMS(m/z ): [M+Na]+ calcd for [C30 H20 O4 Na]+ , 467.12538; found, 467.12699. elemental analysis
(% calcd, %) found for C30 H20 O4 ): C (81.07, 81.19), H (4.54,4.86), O (14.40, 13.95)

Synthesis, HPLC, CD and optical rotation analyses of FRCs. A 20 mL methanol solution

of TREN (58 mg, 0.4 mmol) was layered onto a 20 mL DCM solution of ETTBA (133.2 mg, 0.3
mmol), and the biphasic reaction mixture was allowed to stand at ambient temperature without
stirring. After 10 days, the FRCs were formed in both solutions and crystals, and were further
collected for the HPLC separation (yield 99.8%). The HPLC separation was performed on a
Shimadzu LC-16A instrument with a Daicel Chiralcel IC Column, by using the mobile phase of
chloroform: methanol: toluene = 30:50:20 (v/v/v) at a flow rate of 0.6 mL min−1 . Detection for
HPLC analysis was conducted at 300 nm.
All CD spectra of the separated stereoisomers were measured in dichloromethane: methanol =
1:1 (v/v) at the concentration of 10 µM.
The optical rotations of isolated compounds were also measured with an automatic polarimeter
298K
(SGW-2): [α]D ((6M )-1) = 872.35 ◦ cm2 g−1 , [α]298K
D ((2P 4M )-2) = 506.81 ◦ cm2 g−1 , [α]298K
D ((6P )-
1) = -859.82 ◦ cm2 g−1 , [α]298K
D ((4P 2M )-2) = -510.32 ◦ cm2 g−1 .

Single-crystal X-ray diffraction. To obtain the single crystals, the separated FRCs from HPLC
were individually dissolved into chloroform (1 mL) and layered with diethyl ether (1 mL) on top.
The cube crystals of (6M )-1 and (6P )-1, and the hexagonal crystals of (4P 2M )-2 and (2P 4M )-2
were grown within two to seven days.
Single crystal X-ray diffraction data were collected on Rigaku SuperNova X-Ray single crystal

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diffractometer using Cu Kα (λ = 1.54184 Å) micro-focus X-ray sources. The crystals cracks within
seconds in air due to their large empty structures. Relatively large crystals (0.2×0.2×0.2 mm3
or 0.1×0.1×0.1 mm3 ) were collected at 0 ◦ C, covered with protective oil and mounted on X-ray
diffractometer immediately. For high θ angle collection, more exposure time was given. The similar
procedures were carried for another three crystals. The crystals were kept in 150 K or 223 K with
liquid nitrogen stream during the unit cell determination and full data collection.
The raw data were collected and reduced by CrysAlisPro software. the structures were solved
by the SHELXT [1] with Intrinsic Phasing or SHELXD [1] with Dual Space and refined on F 2
by full-matrix least-squares methods with the SHELXL [1] and OLEX2 [2] was used as GUI. The
detailed crystal parameters are listed in the Supplementary Tab. 1, and the ORTEP drawings are
shown in the Figs. S13-S16.
Refinement details: For each crystal of (6M )-1, (6P )-1, (2P 4M )-2 and (4P 2M )-2, all
nonhydrogen atoms were refined anisotropically. Hydrogen atoms were placed at calculated
positions using the riding model and refined isotropically. The instructions AFIX 23 and AFIX
43 were used for the hydrogen atoms on the secondary -CH2 - and the aromatic C-H, respectively,
with the parameter of Uiso = 1.2 Ueq . For (6M )-1 and (6P )-1, atoms of ethylene group and one
imine group at the vertex were significantly disordered. Therefore, necessary Shelx restraints (i.e.,
DELU, SIMU and DFIX) were applied to these atoms to result a reasonable model. Specifically,
the anisotropic displacement parameters of disordered atoms were restrained to be equal within
an effective standard deviation of 0.001 using the DELU command. Uij values of disordered atoms
were constrained to be similar using the SIMU command. Some unreasonable bond length in vinyl
bonds and imine bonds were restrained using the DFIX command (C=C:1.34 0.01, C-C: 1.54 0.01,
C=N: 1.34 0.01). The remaining solvent molecules within the lattice those were highly disordered,
especially for those in the large void of cube. A satisfactory disorder model for the solvent molecules
was not found, therefore the OLEX2 Solvent Mask routine (similar to PLATON/SQUEEZE) was
used to mask out the disordered density.
Note that, the absolute configuration of each FRCs in crystal was assigned by comparing the
and (ZINDO/S)-predicted CD spectra to the experimental CD spectra, instead of anomalous
dispersion effects in diffraction measurements on the crystal and the derived Flack x parameter.The
cage crystal contains only light atoms (N, O, C, H) and has large void regions, therefore its
extremely difficult to determine the absolute configuration by the Flack x parameter with such
large uncertainty. However,the (ZINDO/S)-predicted CD spectra by using crystal structures highly
matched the experimental ones as shown in the Fig. S8. Therefore, this evidence can be used to
determine the absolute configuration of the FRCs.

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Computational methods.
Calculation of CD spectra: CD spectra were calculated at ZINDO [3, 4] semi-empirical level
with Gaussian 09 [5] and used the optimized crystal structures. The electronic transitions were
then fitted to a Lorentzian distribution to generate the spectra.

DFTB+ calculation: The dual emergent properties of FRCs are clearly resulted from the
restriction of the intramolecular flipping of the TPE faces[6, 7]. Nevertheless, it remains an open
question why the restriction of flipping can be achieved in FRCs, since FRCs also have large
structures and weak steric hindrance between the opposite TPE faces. To this end, we performed
the density functional based tight binding plus (DFTB+) calculations to compare the potential
energy surfaces (PES) of the phenyl flipping in free TPE monomer and in (6M )-1[8, 9].
The PES for TPE monomer was constructed by synchronously flipping the four phenyl rings
with increasing the CP h -CP h -C=C dihedral angle from 22.5 to 157.5◦ , and the flipping energy
barrier was calculated to be 53.9 kJ mol−1 (Figs. S11A and S11B). Therefore, the interconversion
between (M )-TPE and (P )-TPE can happen at room temperature, and hence the TPE monomer
is neither fluorescent nor chiroptical active in dilute solution. By contrast, if one of the six TPE
faces in (6M )-1 was flipped into P configuration (pathway in Fig. S11C), the energy of the resulted
5M 1P structure would be 58.8 kJ mol−1 higher than that of (6M )-1, and the energy barrier from
(6M )-1 to 5M 1P is much larger than that in the reverse direction. Therefore, when one TPE face
in (6M )-1 was flipped, it will easily flip back to the original (6M )-1 structure. Furthermore, the
complete interconversion from (6M )-1 to (6P )-1 involves the flipping of all 24 phenyl rings (Fig.
S11D). The energy barrier of this pathway was calculated to be 224.9 kJ mol−1 , thus explaining
the remarkable stability of (6M )-1 against racemization.
In addition, DFTB+ calculations showed that every imine bond followed the flipping of its
attached phenyl ring and kept in the same plane of the phenyl ring during the flipping of TPE
faces (S12). This suggests that the strong conjugation between the imine bonds and the attached
phenyl rings also contributes to high energy barrier of the interconversion of FRCs. Therefore,
the cooperativity in the six TPE faces and the conjugation between imine bonds and phenyl rings
work together to realized the restriction of flipping in FRCs and thus to generate the emergent
chirality and fluorescence.

DFTB+ calculation detail: The TPE monomer structure was constructed directly to follow
a D2 symmetry, and further optimized to the initial structure with the CP h -CP h -C=C dihedral
angle of 42.5◦ . Crystal structure of (6M )-1 was adjusted to follow the T symmetry, and further
optimized to the initial structure with two kinds of CP h -CP h -C=C dihedral angles, i.e., 45◦ and 50◦ ,
as shown in Fig. S12a. The calculated dihedral angles are smaller than that in crystals (Fig. S5a),

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and this can be rationalized by the difference of the lowest energy structures in solid and solution
states.
The initial structures of TPE and (6M )-1 were further adjusted to other structures by rotating
the certain phenyl groups, as shown in Fig. 5 and Fig. S12. All the structural optimization
and energy calculation were carried out by the DFTB+ [10] module in Materials Studios 7.0 as
a licensed product of BIOVIA. The divide and conquer eigensolver, CHNO Slater-Koster library
and smart algorithm were used within ultrafine calculation quality (0.01 kcal mol−1 energy, 0.05
kcal mol−1 Å−1 Force, 5 × 10−4 Å displacement with 3000 iterations for convergence tolerance).
No motion group was assigned for the initial structures of TPE monomer and (6M )-1, whereas
the TPE units with fixed CP h -CP h -C=C dihedral angles were assigned as the rigid motion groups
during the calculations.

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Supplementary References

[1] Sheldrick, G. M. Acta Crystallogr. Sect. C 2015, 71, 3–8.

[2] Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J. K.; Puschmann, H. J. Appl. Crystallogr. 2009,
42, 339–341.

[3] Telfer, S. G.; Tajima, N.; Kuroda, R.; Cantuel, M.; Piguet, C. Inorg. Chem. 2004, 43, 5302–
5310.

[4] Telfer, S. G.; Tajima, N.; Kuroda, R. Journal of the American Chemical Society 2004, 126,
1408–1418.

[5] Frisch, M.; Trucks, G.; Schlegel, H.; Scuseria, G.; Robb, M.; Cheeseman, J.; Scalmani, G.;
Barone, V.; Mennucci, B.; Petersson, G.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.;
Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.;
Izmaylov, A. F.; Sonnenberg, J. L. Gaussian 09 revision B.01. 2010.

[6] Wang, J.; Mei, J.; Hu, R.; Sun, J. Z.; Qin, A.; Tang, B. Z. J. Am. Chem. Soc. 2012, 134,
9956–9966.

[7] Shustova, N. B.; Cozzolino, A. F.; Dincǎ, M. J. Am. Chem. Soc. 2012, 134, 19596–19599.

[8] Shustova, N. B.; Ong, T.-C.; Cozzolino, A. F.; Michaelis, V. K.; Griffin, R. G.; Dincǎ, M. J.
Am. Chem. Soc. 2012, 134, 15061–15070.

[9] Zhang, C.; Wang, Z.; Tan, L.; Zhai, T. L.; Wang, S.; Tan, B.; Zheng, Y. S.; Yang, X. L.;
Xu, H. B. Angew. Chem. Int. Ed. 2015, 54, 9244–9248.

[10] Aradi, B.; Hourahine, B.; Frauenheim, T. J. Phys. Chem. A 2007, 111, 5678–5684.

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