Supporting Information

for

Insight into the Clustering-Triggered Emission

and Aggregation-Induced Emission Depicted
by an Adamantane-Based Molecular System

Wenjun Xu,1 Dingfang Hu,1 Zhaolong Wang,1 Gang Wang,1 Ke Liu,1 Jingjing Liang,1

Rong Miao*, 1 and Yu Fang*, 1

1 Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education,

School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an

710062, P. R. China

Corresponding Author

*(R. M.) E-mail: [email protected].

*(Y. F.) E-mail: [email protected].

S1
Contents

1. Experimental Section
2. Synthetic Details
3. Number Densities of Cb-Ph in the Crystals
4. Supplementary Figures and Tables
5. NMR and MS Spectra of Intermediates and Target Molecule
6. References

S2
1. Experimental Section
Materials All solvents and reagents with at least analytical grade were purchased
from commercial sources and used without further purification. Solvents of reagent
grade were distilled before use. Column chromatography was performed on silica
(silica gel, 200-300 mesh). All reactions mentioned in experimental details of SI
were performed under argon atmosphere using standard Schlenk and glovebox
techniques.

Instrumental Methods 1H NMR and 13C NMR spectra were recorded on a Bruker
AV 600 NMR spectrometer at room temperature, and referenced externally to TMS.
High-resolution mass spectra (HRMS) were collected on a Bruker maXis UHR-
TOF mass spectrometer in an APCI positive mode. Part of the MS data were
collected on a Bruker maxis MALDI-TOF mass spectrometer in an ESI positive
mode. The purities and structures of the compounds were confirmed by analyzing
the messages from NMR and HRMS. UV-vis spectra were recorded on a Hitachi
U-3900/3900H spectrophotometer and the molar absorption coefficients of all the
compounds were calculated using the equation A = εbc named as Beer–Lambert
law, where A is the absorbance, ε is the molar absorption coefficient, b is the length
of cell, and c is the concentration of the compound under study. Steady-state
fluorescence excitation and emission spectra were performed on Edinburgh FLS
920 fluorescence spectrometer. All solvents used in the test were distilled and did
not fluoresce. The water used in this work was purified from a Milli-Q system. The
optical images depicted in the paper were recorded using a Canon 70D camera.

Synthesis of Ad-4CP, Cb-Ph and Related Intermediates The synthetic intermediate

TIPA was prepared according to literature methods,1and TIPA-Ar was prepared in
the ways through utilization of the famous Sonogashira coupling reaction, where
the tertiary butyl was introduced to increase the solubility of the precursors to allow
facile synthesis. The final compound (Ad-4CP) and the reference fluorophore (Cb-
Ph) were synthesized according to a known method for preparing o-carborane
derivatives.2
S3
X-ray Crystallography Analysis Single crystals of Ad-4CP and the reference
compound (Cb-Ph) were obtained from THF/n-hexane and THF/methanol solution,
respectively. All data were obtained using a Bruker D8 VENTURE Metaljet
PHOTON II diffractometer using Mo/Ga Kα radiation. The crystal was kept at 193
K during data collection. Using Olex2, the structure was solved with the SHELXT
structure solution program using Intrinsic Phasing and refined with the XL
refinement package using Least Squares minimization.

Theoretical Calculation The geometry optimizations of Cb-Ph and Ad-4CP in the

ground state and excited state were performed at the density functional level of
theory (DFT) using the B3LYP functional and a 6-31G(d) basis set, implemented
by Gaussian 09 in gaseous phase. The frontier molecular orbitals were obtained
from the optimized geometry at DFT/B3LYP/6-31G(d) level in Gauss View
software program (version 5.0).

S4
2. Synthetic Details

Scheme S1 Synthesis of the target fluorophore, Ad-4CP.

Scheme S2 Synthesis of the control fluorophore, Cb-Ph.

Synthesis of TIPA The intermediates TIPA was synthesized following the method
described in ref. 1.1 1H NMR (CDCl3, 600 MHz, ppm): δ 7.66 (d, 8H), 7.17 (d, 8H),
2.05 (s, 12H). HRMS (APCI-Orbitrap) m/z: [M] calc. for C34H28I4 943.8364; found
943.8356.

Synthesis of TIPA-Ar This compound was synthesized following conventional

Sonogashira coupling reaction method. The solution of TIPA (100 mg, 0.10 mmol), 4-
(Tert-butyl) phenylacetylene (0.10 mL), PdCl2(PPh3)2 (7.02 mg, 0.01 mmol) and CuI
(1.90 mg, 0.01 mmol) in 20 mL dichloromethane and 10 mL triethylamine was stirred
for 48 hours at 65 ℃ under nitrogen atmosphere. Then, the solution was evaporated in
vacuum and the resulting residue was purified by column chromatography on silica gel

S5
using n-hexane/dichloromethane (4:1, v/v) as eluent. TIPA-Ar was obtained as a white
solid. 1H NMR (CD2Cl2, 600 MHz, ppm): δ 7.47-7.43 (m, 16H), 7.37 (d, 8H), 7.30 (d,
8H), 2.11 (s, 12H), 1.24 (s, 36H). MS (MALDI-TOF) m/z: [M+H]+ calc. for C82H81
1065.63; found 1065.68.

Synthesis of Ad-4CP Ad-4CP was synthesized according to a known literature

method.2 A mixture of decaborane (B10H14, 52.7 mg, 0.47 mmol), TIPA-Ar (100 mg,
0.094 mmol) and N, N-dimethylaniline (22.76 mg, 0.19 mmol) in distilled toluene (4
mL) was stirred at room temperature for 30 min under N2 atmosphere, and then the
temperature was raised to 120 °C for 8 h. Then, the solution was evaporated in vacuum
and the resulting residue was purified by column chromatography on silica gel using n-
hexane/dichloromethane (4:1, v/v) as eluent. Ad-4CP was obtained as a pale-yellow
solid. 1H NMR (CD2Cl2, 600 MHz, ppm): δ 7.25 (d, 8H), 7.22 (d, 8H), 7.02 (d, 8H),
6.98 (d, 8H), 1.64 (s, 12H), 1.06 (s, 36H). MS (MALDI-TOF) m/z: [M+H]+ calc. for
C82H91B10 1545.63; found 1545.16.

Synthesis of Cb-Ph A mixture of decaborane (B10H14, 94 mg, 0.84 mmol), Benzene, 1,

1'-(1,2-ethynediyl)bis[4-(1,1-dimethylethyl)- (100 mg, 0.34 mmol) and N, N-
dimethylaniline (83.6 mg, 0.69 mmol) in distilled toluene (5 mL) was stirred at room
temperature for 30 min under N2 atmosphere, and then the temperature was raised to
120 °C for 5 h. Then, the solution was evaporated in vacuum and the resulting residue
was purified by column chromatography on silica gel using petroleum ether as eluent.
Cb-Ph was obtained as a white solid. 1H NMR (CD2Cl2, 600 MHz, ppm): δ 7.24 (d,
4H), 7.06 (d, 4H), 1.10 (s, 18H). MS (MALDI-TOF) m/z: [M+K]+ calc. for C22H36B10K
448.34; found 448.43.

S6
3. Number Densities of Cb-Ph in the Crystals

As determined from the X-ray diffraction measurements (Table S2, Table S3), the
densities of Cb-Ph and Ad-4CP are 1.065 g/cm3 and 1.002 g/cm3, respectively. The
molecular weight of Cb-Ph is 408.61 g/mol, and the converted unit weight of Cb-Ph
in Ad-4CP is 384.54 g/mol. Based on the data, it can be calculated that the number
densities of Cb-Ph in the two crystals are the same, which is ~2.61 mmol/cm3.

S7
4. Supplementary Figures and Tables

Figure S1 Concentration-dependent UV-vis absorption spectra of Ad-4CP (a) and

Cb-Ph (b) recorded in THF at 298 K. Inset: Plots of absorbance versus
concentration at 297 nm and 285 nm, respectively.

S8
Figure S2 Fluorescence emission spectra of Cb-Ph in benzene and THF at 2.0×10-5
mol/L excited at different wavelengths.

S9
Figure S3 Fluorescence excitation spectra and emission spectra of a frozen Cb-Ph
solution (full lines) at a concentration of 2×10-4 M in THF at 150 K. The dotted line
represents the emission spectrum of Ad-4CP at a concentration of 5×10-5 M in THF
at 298 K.

S10
Figure S4 The photos of Ad-4CP (top, reference Video S1) and Cb-Ph (bottom,
reference Video S2) upon excitation and after removal of excitation source excited

at 254 nm UV in frozen THF solution.

S11
Figure S5 Normalized UV-vis absorption spectra of solutions recorded in THF and
the powders at 298 K.

S12
Figure S6 o-Carboranyl C–C bond distance (Å) and torsion angle (°) for Cb-Ph
and Ad-4CP measured with Mercury software.

S13
Figure S7 The distance of C-H…π between tertiary butyl and the π-plane of
benzene ring in Cb-Ph measured with Mercury software.

S14
Figure S8 The color calibration of reduced density gradient (RDG) analysis with
different intermolecular interactions.3

S15
Figure S9 Molecular structure of Ad-4CP obtained by X-ray diffraction.

S16
Figure S10 Molecular structure of Cb-Ph obtained by X-ray diffraction.

S17
 Table S1 The common strong intermolecular interactions in Cb-Ph and Ad-4CP.

Intermolecular
Distance* Cb-Ph Ad-4CP
interaction

---- ----
π-π stacking 3.3-3.6 Å
(No overlapped π planes) (No overlapped π planes)

----
3.323 Å
C-H…π 2.6-3.0 Å (C–H bond pointing outside
(Reference Fig. S4)
the benzene ring)

---- ----
B-H…π 2.4-2.7 Å (B–H bond pointing outside (B–H bond pointing outside
the benzene ring) the benzene ring)

……

* Distances required for formation of meaningful inter-moiety supramolecular interactions (no

matter intramolecular and intermolecular).4-7

S18
 Table S2 Crystallographic data of Ad-4CP.

Identification code Ad-4CP

Empirical formula C82H120B40

Formula weight 1538.17

Temperature/K 193
Crystal system tetragonal

Space group P-421c

a/Å 16.8367(7)
b/Å 16.8367(7)
c/Å 17.9855(11)
α/° 90
β/° 90
γ/° 90
3
Volume/Å 5098.4(5)

Z 2
3
ρcalcg/cm 1.002

-1
μ/mm 0.050

F(000) 1624.0
3
Crystal size/mm 0.12 × 0.1 × 0.1

Radiation MoKα (λ = 0.71073)

2Θ range for data collection/° 4.53 to 50.698
Index ranges -20 ≤ h ≤ 19, -20 ≤ k ≤ 16, -21 ≤ l ≤ 20
Reflections collected 38929

Independent reflections 4669 [Rint = 0.1015, Rsigma = 0.0618]

Data/restraints/parameters 4669/378/379
2
Goodness-of-fit on F 1.058

Final R indexes [I>=2σ (I)] R1 = 0.0975, wR2 = 0.2258

Final R indexes [all data] R1 = 0.1940, wR2 = 0.2776

S19
 -3
Largest diff. peak/hole / e Å 0.22/-0.16

Flack parameter 7(10)

S20
 Table S3 Crystallographic data of Cb-Ph.

Identification code Cb-Ph

Empirical formula C22H36B10

Formula weight 408.61

Temperature/K 193.00
Crystal system tetragonal

Space group I41

a/Å 12.5660(5)
b/Å 12.5660(5)
c/Å 16.1388(9)
α/° 90
β/° 90
γ/° 90
3
Volume/Å 2548.4(2)

Z 4
3
ρcalcg/cm 1.065

-1
μ/mm 0.242

F(000) 872.0
3
Crystal size/mm 0.12 × 0.1 × 0.1

Radiation GaKα (λ = 1.34139)

2Θ range for data collection/° 19.434 to 120.586
Index ranges -15 ≤ h ≤ 16, -16 ≤ k ≤ 16, -19 ≤ l ≤ 20
Reflections collected 15635

Independent reflections 2792 [Rint = 0.0518, Rsigma = 0.0327]

Data/restraints/parameters 2792/1/148
2
Goodness-of-fit on F 1.079

Final R indexes [I>=2σ (I)] R1 = 0.0498, wR2 = 0.1348

Final R indexes [all data] R1 = 0.0516, wR2 = 0.1370

S21
 -3
Largest diff. peak/hole / e Å 0.43/-0.23

Flack parameter 0.2(3)

S22
5. NMR and MS Spectra of Intermediates and Target Molecule

Figure S11 1H NMR spectrum of TIPA (600 MHz, CDCl3).

S23
Figure S12 MS spectrum of TIPA.

S24
Figure S13 1H NMR spectrum of TIPA-Ar (600 MHz, CD2Cl2).

S25
Intens. [a.u.]
1065.68

150

1064.67
125

100

1066.66

75

50

1067.70

25

0
1064.0 1064.5 1065.0 1065.5 1066.0 1066.5 1067.0 1067.5 1068.0 1068.5
m/z

Figure S14 MS spectrum of TIPA-Ar.

S26
Figure S15 1H NMR spectrum of Ad-4CP (600 MHz, CD2Cl2).

S27
Intens. [a.u.]
1545.16
1500
1544.19

1546.18

1250

1543.19

1000
1547.17

750
1542.14

1548.17

500

1541.23
1549.17

250

0
1536 1538 1540 1542 1544 1546 1548 1550 1552 1554
m/z

Figure S16 MS spectrum of Ad-4CP.

S28
Figure S17 1H NMR spectrum of Cb-Ph (600 MHz, CD2Cl2).

S29
Intens. [a.u.]
250 448.43

449.43

200

447.43

150

450.42

100

446.43

50

445.45 451.46

0
445 446 447 448 449 450 451 452
m/z

Figure S18 MS spectrum of Cb-Ph.

S30
6. References
[1] Zulfiqar, S.; Mantione, D.; El Tall, O.; Sarwar, M. I.; Ruipérez, F.; Rothenberger,
A.; Mecerreyes, D., Nanoporous Amide Networks Based on
Tetraphenyladamantane for Selective CO2 Capture. J. Mater. Chem. A 2016, 4,
8190-8197.
[2] Liu, K.; Shang, C.; Wang, Z.; Qi, Y.; Miao, R.; Liu, K.; Liu, T.; Fang, Y., Non-
Contact Identification and Differentiation of Illicit Drugs Using Fluorescent Films.
Nat. Commun. 2018, 9, 1695.
[3] Lu, T.; Chen, Q., Interaction Region Indicator (IRI): A Simple Real Space Function
Clearly Revealing Both Chemical Bonds and Weak Interactions. Chemistry—
Methods, 2021, 1, 231-239.
[4] Mishra, K. B.; Sathyamurthy, N., π-π Interaction in Pyridine. J. Phys. Chem. A
2005, 109, 6-8.
[5] Steed,W. J.; Atwood, L. J., Supramolecular Chemistry, 2nd edition, John Wiley &
Sons, Ltd, 2009.
[6] Nishio, M., The CH/π Hydrogen Bond in Chemistry. Conformation,
Supramolecules, Optical Resolution and Interactions Involving Carbohydrates.
Phys. Chem. Chem. Phys. 2011, 13, 13873-13900.
[7] Zhao, C.; Parrish, R. M.; Smith, M. D.; Pellechia, P. J.; Sherrill, C. D.; Shimizu,
K. D., Do Deuteriums Form Stronger CH-π Interactions? J. Am. Chem. Soc. 2012,
134, 14306-14309.

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