Supporting Information for:

A New Topological Class of Interlocked and Interwoven Nanocarbons via Dynamic C-C
Bond Formation

Harrison M. Bergman,1 Angela Fan,1 Christopher G. Jones,2,3 August J. Rothenberger,1 Kunal K.

Jha,3 Rex C. Handford,1 Hosea M. Nelson,2,3 Yi Liu,4 T. Don Tilley1
1
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States
2
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095,
United States
3
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125,
United States
4
Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

General details ...............................................................................................................................S1

Synthetic procedures and basic characterization data ...................................................................S2
Evidence that Product Formation of 3-Zr is not Driven by Precipitation .....................................S10
Optimization of 3-Zr Synthesis ...................................................................................................S11
1
H NMR Study of Monomer-Dimer Equilibria ...........................................................................S12
In-Depth Topological Discussion of Perplexanes ........................................................................S14
1
H and 13C{1H} NMR Spectra .....................................................................................................S16
MALDI-TOF Spectrometry ........................................................................................................S28
Absorption and Emission spectroscopy .......................................................................................S30
X-ray Crystallography .................................................................................................................S31
References ...................................................................................................................................S34

General Details

Unless otherwise stated, all manipulations were conducted in dry solvents under an inert
atmosphere of nitrogen, using either standard Schlenk techniques or a glovebox. Pentane, toluene,
tetrahydrofuran (THF), and diethyl ether, were dried using a JC Meyers Phoenix solvent
purification system. Thiophene, hexamethyldisiloxane (HMDSO), C6D6, and CDCl3 were freed
from oxygen with vigorous nitrogen bubbling for 30 minutes, and then dried for at least 48 h over
3 Å molecular sieves (5% by mass). All reaction solvents were stored over 3 Å molecular sieves.
S1,1 S3,2 1-mon,3 and Cp2Zr(pyr)(Me3SiC≡CSiMe3)4 were synthesized by literature procedures.
All other reagents were purchased from commercial suppliers and used as received. “Room
temperature” or “RT” refers to ~22 ˚C. Reaction temperatures represent the oil bath temperature
unless otherwise stated. Mass spectrometry of all compounds except 2 and 3 (see MALDI-TOF
Spectrometry for details) was performed by the QB3/Chemistry Mass Spectrometry Facility at the
University of California, Berkeley. Column chromatography was carried out using Fisher
Chemical 40–63µm, 230–400 mesh silica gel. NMR (1H and 13C) spectra were obtained at room
temperature on Bruker Avance 400, 500, and 600 MHz spectrometers. Chemical shifts (δ) are
given in ppm and are referenced to residual solvent peaks for 1H-NMR spectra (δ = 7.26 ppm for

S1
CDCl3 and δ = 7.16 for C6D6) and 13C-NMR spectra (δ = 77.16 ppm for CDCl3, δ = 128.06 for
C6D6, and δ = 67.21 for THF-d8).

Synthetic procedures and basic characterization data

S
SiMe3 H SiMe2R
SiMe3
nBuLi, ZnCl2, Me2RSiCl
Pd(PPh3)4 K2CO3 NaHMDS

THF, -78 to 60 ˚C MeOH/H2O, 50 ˚C THF, 23 ˚C

84% 99%
Br S S S

S1 S2 S3 R = Bu; S4; 91%

R = Oct; S5; 90%
Scheme S1. Synthesis of linkers S2, S4, and S5.

S2. Degassed thiophene (4.65 g/4.43 mL, 0.055 mol, 1.4 eq) and THF (250 mL) was added to a
dry schlenk flask under N2. Reaction mixture was cooled to -78°C with a CO2/isopropanol bath
and n-BuLi (1.6 M in hexanes, 32.1 mL, 0.05 mol, 1.3 eq) was added via syringe to the solution
over 10 minutes. After stirring for 10 minutes, ZnCl2 (1.04 M in THF, 59.2 mL, 0.062 mol, 1.56
eq) was added via syringe over 2 minutes. The reaction mixture was then warmed back to room
temperature. Once at RT, AF-2 (10 g, 0.04 mol, 1 eq) and Pd(PPh3)4 (2.31 g, 0.002 mol, 0.05 eq)
was added to the flask against the flow of N2, heated at 65°C, and stirred for 12hrs. The reaction
mixture was then cooled to RT and quenched with ammonium chloride. This crude mixture was
then extracted with CH2Cl2, dried over MgSO4, and solvents were removed with rotary
evaporation. The crude product was purified via filtration and a silica plug (20% DCM in hexanes)
to afford S2 as a colorless powder (7.7g, 84% yield). The 1H NMR spectrum of this material
matched the reported data.2
1
H NMR (400 MHz, chloroform-d) δ 7.55 (d, J = 8.5 Hz, 1H), 7.46 (d, J = 8.5 Hz, 1H), 7.33 (dd,
J = 3.6, 1.1 Hz, 1H), 7.30 (dd, J = 5.1, 1.0 Hz, 1H), 7.08 (dd, J = 5.1, 3.6 Hz, 1H), 0.26 (s, 27H).

S4. To a 50 mL Schlenk flask was added S3 (1.40 g, 7.60 mmol, 1.00 equiv) and THF (30 mL). A
solution of sodium hexamethylsilazine (1.46 g, 7.98 mmol, 1.05 equivs) in THF (10 mL) was
added slowly at RT and stirred for 10 min. Dimethylbutylchlorosilane (1.72 g, 11.4 mmol, 1.5
equivs) was subsequently added against N2, and the reaction mixture was stirred for 1 h at RT.
Aqueous ammonium chloride was then added and the reaction mixture was extracted with DCM
(3x10 mL), dried with MgSO4, and solvents were removed via rotary evaporation. The crude
product was purified by column chromatography (100% hexanes) to afford S4 (2.06 g, 91%) as a
pale yellow oil. 1H NMR (600 MHz, Chloroform-d) δ 7.58 – 7.52 (m, 2H), 7.49 – 7.44 (m, 2H),
7.33 (dd, J = 3.6, 1.2 Hz, 1H), 7.30 (dd, J = 5.1, 1.2 Hz, 1H), 7.09 (dd, J = 5.1, 3.6 Hz, 1H), 1.48
– 1.35 (m, 4H), 0.93 (m, 3H), 0.74 – 0.63 (m, 2H), 0.23 (s, 6H). 13C NMR (151 MHz, CDCl3) δ
143.80, 134.49, 132.64, 128.31, 125.65, 125.55, 123.74, 122.27, 105.39, 94.77, 77.37, 77.16,
76.95, 26.40, 26.20, 16.06, 13.96, -1.53. ESI-MS (m/z): [M]+ calcd. for C18H22SSi, 298.1211;
found, 298.1217.

S2
S5. This compound was synthesized and purified according to the procedure outlined above for
S4 using the following amounts: S3 (700 mg, 3.80 mmol) in 15 mL THF, sodium
hexamethylsilazine (730 mg, 3.99 mmol) in 5 ml THF, Dimethyloctylchlorosilane (1.18 g, 5.70
mmol) to afford S5 (1.21 g, 3.42 mmol) as a viscous yellow oil. 1H NMR (400 MHz, Chloroform-
d) δ 7.57 – 7.51 (m, 2H), 7.48 – 7.43 (m, 2H), 7.33 (dd, J = 3.7, 1.2 Hz, 1H), 7.30 (dd, J = 5.1, 1.1
Hz, 1H), 7.08 (dd, J = 5.1, 3.6 Hz, 1H), 1.50 – 1.16 (m, 12H), 0.93 – 0.83 (m, 3H), 0.73 – 0.64 (m,
2H), 0.22 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 143.79, 134.48, 132.63, 128.29, 125.63, 125.53,
123.72, 122.27, 105.42, 94.79, 77.37, 77.16, 76.95, 33.43, 32.10, 29.48, 29.43, 23.99, 23.95, 22.85,
16.33, 14.27, -1.51. ESI-MS (m/z): [M]+ calcd. for C22H30SSi, 354.6270; found, 354.6269.

BuMe2Si

S
S SiMe2Bu
N
N N

BuMe2Si 2-mon
2-mon. A 125 mL Schlenk flask was charged with S4 (2.00 g, 6.70 mmol, 3.30 equiv) and
tetrahydrofuran (25 mL) and the solution was cooled to –78 °C with a CO2(s)/acetone bath. To this
solution was added n-butyllithium (1.85 M in hexanes, 3.99 mL, 6.50 mmol, 3.20 equiv) by
syringe over 5 min and the resulting mixture was stirred for a further 1 h at –78 °C. To this mixture
was added ZnCl2 (1.05 M in THF, 6.57 mL, 6.90 mmol, 3.4 equiv) by syringe over 5 min, and
subsequently the flask was removed from the cold bath and warmed to RT over 1 h. At this time
tris(4-bromophenyl)-1,3,5-triazine (1.11 g, 2.03 mmol, 1.00 equiv) and Pd(PPh3)4 (234 mg, 0.203
mmol, 0.100 equiv) were added against a flow of N2, the Schlenk flask was sealed, and the mixture
was heated to 65 ˚C and stirred for 18 h. The solution was then exposed to air and diluted with
aqueous ammonium chloride (40 mL). The crude product was extracted with CH2Cl2 (3x 20 mL),
dried over MgSO4, and solvents were removed by rotary evaporation. The crude product was
purified by gradient column chromatography (from 15 to 40% CH2Cl2 in hexanes) and solvent was
removed by rotary evaporation to afford 2-mon (1.58 g, 65%) as a bright yellow powder. 1H NMR
(400 MHz, Chloroform-d) δ 8.79 (d, J = 8.4 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.61 (d, J = 8.4

S3
Hz, 2H), 7.50 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 3.8 Hz, 1H), 7.37 (d, J = 3.8 Hz, 1H), 1.43 (dd, J =
7.8, 3.7 Hz, 4H), 0.93 (t, J = 6.9 Hz, 3H), 0.75 – 0.67 (m, 2H), 0.24 (s, 6H). 13C NMR (151 MHz,
CDCl3) δ 170.21, 143.55, 143.38, 137.41, 134.96, 134.09, 132.61, 129.34, 125.22, 125.14, 124.98,
124.74, 122.33, 105.49, 94.99, 77.37, 77.16, 76.95, 26.45, 26.25, 16.11, 14.02, -1.44. MS-MALDI
(m/z): [M]+ calcd. for C75H75N3S3Si3, 1197.4431; found, 1197.4427.

Me3Si

S
S SiMe3

Me3Si 3-mon

3-mon. This compound was synthesized according to the procedure outlined above for 2-mon
using the following amounts: S2 (4.00 g, 15.6 mmol, 3.50 equivs), nBuLi (1.85 M in hexanes, 8.27
mL, 15.3 mmol, 3.40 equivs), ZnCl2 (1.05 M in THF, 15.6 mL, 16.2 mmol, 3.60 equivs), 1,3,5-
tribromobenzene (1.42 g, 4.46 mmol, 1.00 equiv), Pd(PPh3)4 (578 mg, 0.50 mmol, 0.1 equiv) and
100 mL THF. The crude product was purified via column chromatography (20% DCM in
hexanes), and subsequent precipitation from a saturated DCM solution with MeOH afforded 3-
mon (3.04 g, 81%) as a very faintly yellow-green powder. 1H NMR (400 MHz, Chloroform-d)
δ 7.77 (s, 3H), 7.64 – 7.56 (m, 6H), 7.53 – 7.46 (m, 6H), 7.42 (d, J = 3.8 Hz, 3H), 7.37 (d, J = 3.8
Hz, 3H), 0.27 (s, 27H). 13C NMR (151 MHz, chloroform-d) δ 143.65, 143.24, 135.69, 134.20,
132.71, 125.41, 125.09, 124.76, 122.42, 122.16, 105.00, 95.63, 77.37, 77.16, 76.95, 0.13. MS-
MALDI (m/z): [M]+ calcd. for C51H48S3Si3, 840.2226; found, 840.2229.

(C8H17)Me2Si SiMe2(C8H17)

N
N N

SiMe2(C8H17)
1-mon-oct

S4
1-mon-oct. A flask was charged with tris(4-bromophenyl)-1,3,5-triazine (0.100 g, 0.183 mmol),
(PPh3)2PdCl2 (0.013g, 0.018 mmol), and copper(I) iodide (0.007 g, 0.037 mmol). Tetrahydrofuran
(5 mL) and triethylamine (2 mL) were then added, followed by ethynyl(dimethyl)octylsilane
(0.126 g, 0.641 mmol). The reaction mixture was stirred at 60 oC for 18 h, then quenched with sat.
NH4Cl (5 mL) and extracted with dichloromethane (3 x 10 mL). The organic fractions were
combined and dried with MgSO4, then the solvent was evaporated and the residual solid dissolved
in hexanes and eluted through a short plug of silica (10 g) with hexanes. The solvent was
evaporated and the yellow solid was recrystallized from methanol to afford 1-mon-oct as pale
yellow crystals (0.134 g, 82%). 1H NMR (600 MHz, chloroform-d): δ = 8.68 (d, J = 8.4 Hz, 6H),
7.64 (d, J = 8.4 Hz, 6H), 1.46 (m, 6H), 1.39 (m, 6H), 1.31 (m, 24H), 0.89 (t, J = 6.9 Hz, 9H), 0.72
(m, 6H), 0.27 (s, 18H) . 13C NMR (151 MHz, chloroform-d) δ = 171.22, 135.90, 132.38, 128.88,
127.67, 105.19, 97.24, 33.43, 32.11, 29.49, 29.44, 23.99, 22.85, 16.26, 14.28, -1.57. MS-MALDI
(m/z): [M]+ calcd. for C57H81N3Si3, 891.5738; found 891.61.
(C8H17)Me2Si

S
S SiMe2(C8H17)
N
N N

(C8H17)Me2Si 2-mon-oct
2-mon-oct. This compound was synthesized according to the procedure outlined above for 2-mon
using the following amounts: S5 (500 mg, 1.36 mmol, 3.20 equiv), nBuLi (1.85 M in hexanes,
0.708 mL, 1.31 mmol, 3.10 equivs), ZnCl2 (1.05 M in THF, 1.33 mL, 1.40 mmol, 3.3 equivs),
tris(4-bromophenyl)-1,3,5-triazine (231 mg, 0.424 mmol, 1.00 equiv), Pd(PPh3)4 (49.0 mg, 0.042
mmol, 0.10 equiv), and 6 mL THF. The crude product was purified via column chromatography
(25% DCM in hexanes) afford 2-mon-oct (423 mg, 73%) as a bright yellow powder. 1H NMR
(500 MHz, Chloroform-d) δ 8.74 (d, J = 8.3 Hz, 2H), 7.82 – 7.75 (m, 2H), 7.61 – 7.56 (m, 2H),
7.49 (d, J = 8.2 Hz, 2H), 7.44 (d, J = 3.8 Hz, 1H), 7.34 (d, J = 3.7 Hz, 1H), 1.51 – 1.18 (m, 12H),
0.89 (t, J = 6.7 Hz, 3H), 0.75 – 0.67 (m, 2H), 0.25 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 170.38,
143.69, 143.40, 137.55, 135.05, 134.10, 132.64, 129.43, 125.26, 125.21, 125.11, 124.78, 122.40,
105.48, 95.06, 77.37, 77.16, 76.95, 33.49, 32.14, 29.53, 29.48, 24.03, 22.88, 16.39, 14.30, 2.81, -
1.43. MS-MALDI (m/z): [M]+ calcd. for C87H99N3S3Si3, 1365.6309; found 1365.6320.

S5
 (C8H17)Me2Si

S
S SiMe2(C8H17)

(C8H17)Me2Si 3-mon-oct
3-mon-oct. This compound was synthesized according to the procedure outlined above for 2-mon
using the following amounts: (500 mg, 1.36 mmol, 3.20 equiv), nBuLi (1.85 M in hexanes, 0.708
mL, 1.31 mmol, 3.10 equivs), ZnCl2 (1.05 M in THF, 1.33 mL, 1.40 mmol, 3.3 equivs), 1,3,5-
tribromobenzene (133 mg, 0.424 mmol, 1.00 equiv), Pd(PPh3)4 (49.0 mg, 0.042 mmol, 0.10 equiv),
and 6 mL THF. The crude product was purified via column chromatography (15% DCM in
hexanes) to afford 3-mon-oct (366 mg, 76%) as a very faintly yellow-green powder. 1H NMR
(600 MHz, Chloroform-d) δ 7.57 (s, 1H), 7.55 – 7.51 (m, 2H), 7.48 (d, J = 8.3 Hz, 2H), 7.24 (d,
J = 3.7 Hz, 1H), 7.22 (d, J = 3.8 Hz, 1H), 1.56 – 1.27 (m, 12H), 0.94 (t, J = 6.9 Hz, 3H), 0.81 –
0.71 (m, 2H), 0.30 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 143.29, 143.09, 135.30, 134.11,
132.64, 125.25, 124.80, 124.58, 122.38, 121.55, 105.45, 95.03, 77.37, 77.16, 76.95, 33.46, 32.12,
29.51, 29.46, 24.01, 22.86, 16.36, 14.29, 2.80, -1.47. MS-MALDI (m/z): [M]+ calcd. for
C72H90S3Si3, 1134.5512; found, 1134.5518.

M
R

R N N R
N M
M
N N
R N R
R R
N N
M
M N N
N N R
R
M = Cp2Zr
R = SiMe3
R R
M
1-Zr
1-Zr. A Schlenk flask was charged with 1-mon, (100 mg, 0.167 mmol) and Rosenthal’s complex,
Cp2Zr(pyr)(Me3SiC≡CSiMe3), (130 mg, 0.251 mmol). Benzene (3 mL) was then added and the
dark purple solution was heated to 100 oC while stirring for 16 h. The heterogeneous reaction
mixture was cooled to room temperature and the precipitate recovered by filtration. The resulting
solid was washed with pentane (3 x 5 mL) to yield the product as a fine yellow powder (0.132 g,
85%). 1H NMR (600 MHz, THF-d8): δ = 8.25 (d, J = 8.25 Hz, 24H), 6.90 (d, J = 8.25 Hz, 24H),

S6
6.40 (s, 60H), -0.35 (s, 108H). 13C NMR (151 MHz, THF-d8): δ = 206.64, 171.16, 151.45, 150.10,
133.55, 130.56, 128.13, 112.47, 67.39, 25.31, 2.88.

R N R
N
N
N N

R N R R
R
N N
N N
N N R
R
R = SiMe3
R
R
1
1. Tetrahedron 1-Zr (0.120 g, 0.032 mmol) was dissolved in THF (5 mL) and to this solution was
added 2 M HCl in dioxane (0.2 mL, 0.4 mmol). The reaction mixture was diluted with sat. Na2CO3
(1 mL) then the product extracted with dichloromethane (3 x 5 mL). The organic layers were
combined, dried with MgSO4, and the solvent evaporated. The residual solid was washed with
MeOH (5 mL) and EtOH (5 mL) to recover the product as a white solid (0.075 g, 98%). 1H NMR
(600 MHz, chloroform-d): δ = 8.41 (d, J = 8.4 Hz, 24H), 7.18 (d, J = 8.4 Hz, 24H), 6.40 (s, 12H),
-0.04 (s, 108H). 13C NMR (151 MHz, chloroform-d) δ = 170.43, 160.67, 146.05, 134.50, 132.19,
129.70, 127.99, 0.47. MS-MALDI (m/z): [M]+ calcd. for C144H168N12Si12, 2401.0746; found
2401.11.

R
M
S R
R
M
N N S
R
S N S R
N N M
S
N S
R S N N S R
N S
R
M S N N
M R
S N
R S
R M
M = Cp2Zr
R = SiMe2Bu R
2-Zr
2-Zr. A Teflon stoppered flask was charged with 2-mon (283 mg, 0.237 mmol, 1.00 equiv) and
Rosenthal’s complex, Cp2Zr(pyr)(Me3SiC≡CSiMe3), (169 mg, 0.358 mmol, 1.51 equiv). Benzene
(7 mL) was then added, and the flask was sealed and heated to 60 ˚C for 16 h. The reaction mixture
was cooled to RT and the crystalline precipitate was collected and washed with benzene (3x2 mL)
to afford 2-Zr (290 mg, 80%) as yellow crystals. 1H NMR (400 MHz, CDCl3): The 1H NMR of
these single crystals (Figure SX) is complex. While the number of Cp and alkylsilane resonances

S7
match the expected symmetry of the structure as determined by X-ray crystallography, the
aromatic region contains only six sharp resonances with the expected integrations (half the
expected 12) in addition to several broad and several small, sharp resonances. Despite this, the
material was used directly in the subsequent step and cleanly furnishes demetalated 2. This
suggests that the unexpected complexity of the aromatic region is a result of slow dynamic
conformational changes on the NMR timescale due to the relative inflexibility of 2-Zr compared
to 2.
R

R
S
R
N N S
R
S N R S
N N
S
N S
R S N N S R
R N S
S N N R
S N
R S
R
R = SiMe2Bu
R
2
2. A 25 mL Schlenk flask was charged with 2-Zr (273 mg, 0.045 mmol, 1.00 equiv), suspended
in THF (5 mL), and stirred at RT. Trifluoroacetic acid (128 mg, 1.125 mmol, 25.0 equiv) was
added dropwise via syringe over 1 min, during which time the solution became homogeneous. The
reaction mixture was quenched with aqueous NaHCO3 (5 mL), extracted with DCM (3x5 mL),
and concentrated to dryness via rotary evaporation. The resulting crude solid was dissolved in
DCM (20 mL), precipitated via addition of MeOH (40 mL), and collected by vacuum filtration.
The solid was washed with MeOH (3x5 mL) and dried to afford 2 (204 mg, 96%) as a bright
yellow powder. 1H NMR (400 MHz, Methylene Chloride-d2) δ 7.99 (d, J = 8.0 Hz, 2H), 7.48 (d,
J = 7.9 Hz, 2H), 7.38 (d, J = 7.8 Hz, 2H), 7.30 (d, J = 7.9 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 7.09
(dd, J = 12.7, 8.0 Hz, 4H), 7.02 – 6.92 (m, 2H), 6.72 (d, J = 7.8 Hz, 2H), 6.52 (d, J = 1.7 Hz, 2H),
6.19 (d, J = 3.7 Hz, 1H), 5.97 (d, J = 3.7 Hz, 1H), 1.46 – 1.38 (m, 5H), 1.35 (dt, J = 7.6, 4.0 Hz,
5H), 1.02 – 0.95 (m, 4H), 0.91 (q, J = 6.3, 5.6 Hz, 4H), 0.67 (d, J = 8.2 Hz, 2H), 0.56 (d, J = 9.5
Hz, 2H), 0.10 (s, 6H) 0.00 (s, 6H). 13C NMR (151 MHz, CD2Cl2) δ 170.18, 169.38, 161.29,
144.87, 143.47, 142.92, 142.47, 142.23, 141.66, 137.73, 137.00, 134.90, 134.29, 133.12, 132.75,
131.31, 131.17, 129.36, 129.10, 128.97, 128.60, 125.47, 125.35, 125.12, 124.61, 124.48, 124.26,
124.06, 123.76, 72.90, 71.66, 62.21, 54.36, 54.18, 54.00, 53.82, 53.64, 43.82, 30.27, 27.27, 27.17,
26.90, 26.83, 17.11, 17.01, 14.29, 14.21, 1.34, -1.02, -1.15. MS-MALDI (m/z): [M]+ calcd. for
C300H312N12S12Si12, 4801.86; found 4801.86.

S8
 R
R M
M R
S R
S
RM S M
S
R
R S S R
S S R
M S M
S
S S R
S
S S
S S
S R
R M
M = Cp2Zr
R R = SiMe3
M R
R
R M
3-Zr
3-Zr. This compound was synthesized according to the procedure outlined above for 2-Zr using
the following amounts: 3-mon (295 mg, 0.350 mmol, 1.00 equiv), Rosenthal’s complex,
Cp2Zr(pyr)(Me3SiC≡CSiMe3), (249 mg, 0.529 mmol, 1.51 equiv), and benzene (6.5 mL) to afford
3-Zr (230 mg, 56%) as a yellow crystalline solid. 1H NMR (600 MHz, THF-d8) δ 7.55 – 7.48 (m,
4H), 7.46 (dd, J = 8.1, 1.9 Hz, 2H), 7.41 (dd, J = 7.9, 2.0 Hz, 2H), 7.35 (dd, J = 8.0, 2.0 Hz, 2H),
7.26 (d, J = 3.6 Hz, 2H), 7.24 (d, J = 3.7 Hz, 2H), 7.15 (d, J = 1.6 Hz, 2H), 7.12 (d, J = 3.8 Hz,
2H), 7.11 – 7.06 (m, 6H), 7.04 (d, J = 8.0 Hz, 2H), 7.03 – 6.98 (m, 4H), 6.94 (dd, J = 8.1, 1.7 Hz,
2H), 6.88 – 6.83 (m, 4H), 6.82 (t, J = 1.6 Hz, 1H), 6.73 (d, J = 1.6 Hz, 2H), 6.67 (s, 9H), 6.65 (t, J
= 1.6 Hz, 1H), 6.53 (s, 11H), 6.47 (s, 8H), 6.15 (d, J = 4.0 Hz, 1H), 5.80 (d, J = 4.0 Hz, 1H), 0.14
(s, 9H), -0.05 (s, 20H), -0.07 (s, 9H), -0.14 (s, 19H).

Note: Unlike for 2-Zr, the concentration plays an important role in product distribution, with
higher concentrations favoring the selective formation of 3-Zr. The concentration used here (54
mM) gave the best results, as discussed in more detail on page SX.

R
R

S R R
S
R S
S
R R S S R
S S R
S
S
S S
R
S
S S
S S
S R
R
R R = SiMe3
R
R
R
3
3. This compound was synthesized according to the procedure outlined above for 2 using the
following amounts: 3-Zr (215 mg, 0.031 mmol, 1.00 equiv), trifluoroacetic acid (88 mg, 0.78
mmol, 25 equiv), and THF (4 mL) to afford 3 (152 mg, 98%) as an off-white powder. 1H NMR
(600 MHz, THF-d8) δ 7.51 (d, J = 8.1 Hz, 2H), 7.46 (d, J = 8.1 Hz, 4H), 7.44 – 7.37 (m, 7H), 7.30
(d, J = 8.2 Hz, 6H), 7.25 – 7.16 (m, 9H), 7.14 – 7.05 (m, 6H), 7.01 – 6.91 (m, 3H), 6.80 – 6.71 (m,
5H), 6.68 – 6.63 (m, 2H), 6.49 (d, J = 10.5 Hz, 4H), 6.15 (d, J = 4.1 Hz, 1H), 5.83 (d, J = 4.1 Hz,

S9
1H), 0.26 (s, 9H), 0.16 (s, 17H), 0.09 (s, 26H). 13C NMR (151 MHz, THF) δ 160.61, 160.32,
159.85, 159.55, 141.05, 140.92, 140.82, 140.65, 140.31, 140.24, 140.07, 140.02, 139.18, 139.04,
138.74, 138.60, 132.15, 132.09, 131.98, 131.76, 131.25, 131.19, 131.13, 131.02, 129.30, 128.68,
128.47, 128.27, 128.06, 123.37, 122.33, 122.10, 121.88, 121.74, 121.59, 121.43, 121.35, 121.17,
121.12, 120.42, 119.70, 116.53, 116.03, 65.05, 64.90, 64.84, 64.69, 64.55, 64.40, 64.26, 27.79,
22.93, 22.80, 22.74, 22.67, 22.60, 22.47, 22.34, 22.20, 20.35, 11.51, -1.85, -2.00, -2.09, -2.18. MS-
MALDI (m/z): [M]+ calcd. for C306H306S18Si18, 5059.47; found 5059.47.

Evidence that Product Formation of 3-Zr is not Driven by Precipitation

Many thermodynamically controlled syntheses of macrocycles and topologically complex

molecules rely on precipitation of the product to increase yield via Le Chatelier’s principle.5-7
Although our synthesis uses product crystallization as a convenient means of in-situ isolation and
purification of the desired products, it is not the thermodynamic driving force for the high yields
observed. To confirm this, we generated 3-Zr in THF rather than benzene, in which the product
does not precipitate. In-situ 1H NMR of this reaction mixtures (Figure S1) illustrates that the
product forms in comparable yield to the isolated yields reported in benzene, showing that the
selectivity observed is inherent to the thermodynamic favorability of product formation in solution.

In-situ reaction mixture Me3Si SiMe3

(THF)
SiMe3
Cp2Zr

Isolated single crystals

(THF-d8)

7 6 0
f1 (ppm)

Figure S1. 1H NMR spectra (500 MHz) of 3-Zr, comparing an in-situ reaction mixture in THF
(top) to isolated single crystals from a reaction in benzene redissolved in THF-d8 (bottom).

S10
Optimization of 3-Zr Synthesis

3-Zr was synthesized at a range of concentrations over one order of magnitude and monitored in-
situ by 1H NMR (Figure S2) to determine the effect of concentration on product distribution.
Although benzene was used as the reaction solvent for isolation, we conducted these experiments
in THF due to its ability to fully solubilize the reaction mixture even at elevated concentration. As
evidenced in the previous section, product distribution and yield appear to be similar between
benzene and THF. In-situ yield was determined by integration of the product Cp peaks against the
bis(trimethylsilyl)acetylene released by Rosenthal’s complex as an internal standard. This study
clearly illustrates that 3-Zr is formed more selectively and in higher yield as concentration is
increased, ostensibly due to the decrease in entropic penalty for the assembly of six monomer units.
This suggests that the competing side products are smaller than 3-Zr.

Me3Si SiMe3
Cp2Zr SiMe3
56.4 mM 5

29.5 mM 4

11.8 mM 3

5.90 mM 2

2.95 mM 1

8 7 6 0
f1 (ppm)

Figure S2. 1H NMR spectra (500 MHz, THF-d8) of in-situ reaction mixtures of 3-Zr at various
concentrations from 2.95 – 56.4 mM to illustrate the effect of monomer concentration on yield and
product distribution.

S11
1
H NMR Study of Monomer-Dimer Equilibrium in 1-mon-oct, 2-mon-oct, and 3-mon-oct

Monomer-dimer equilibria of 1-mon-oct, 2-mon-oct, and 3-mon-oct were investigated by

variable concentration 1H NMR spectroscopy in benzene to mimic the conditions used for product
isolation of 1-Zr, 2-Zr, and 3-Zr respectively. Maximum concentrations were set by solubility
limits of each monomer. Chemical shifts of all aromatic resonances were averaged, this average
was plotted as a function of concentration, and the data was fitted to a monomer-dimer equilibrium
model via the regression approach developed by Moore and coworkers.8-9 Briefly, values for
chemical shift of the monomer (dmon), chemical shift of the dimer (ddim), and equilibrium constant
(Keq) were guessed and fed into the previously developed monomer-dimer model. These values
were used to generate predicted chemical shifts (dp) at each experimental concentration and
compared to the experimental shifts (dexp) to calculate a standard deviation (s). New values for the
three variables were guessed recursively to achieve a local minimum, and the resulting values were
taken. The raw data, final variable values, and predicted chemical shifts are summarized in the
tables S1-S6.

Concentration (M) dexp (ppm) dp (ppm)

0.0782 8.143 8.142
0.0580 8.148 8.148
0.0387 8.153 8.153
0.0258 8.156 8.156
0.0172 8.159 8.159
0.0098 8.161 8.161
0.0049 8.162 8.162
0.0025 8.163 8.163
0.0012 8.163 8.163
Table S1. Experimental concentrations and chemical shifts (dexp) of 1-mon-oct from variable
concentration 1H NMR (500 MHz, C6D6) compared to predicted chemical shifts (dp) from the
monomer–dimer equilibrium model.

dmon (ppm) ddim (ppm) Keq DG˚ (kcal/mol) s

8.163 7.041 0.1240 -1.24 0.0037
Table S2. Optimal monomer–dimer model values to minimize standard deviation between
experimental and predicted values for 1-mon-oct.

Concentration (M) dexp (ppm) dp (ppm)

0.0464 7.346 7.348
0.0281 7.408 7.403

S12
 0.0182 7.443 7.448
0.0129 7.487 7.482
0.0088 7.515 7.515
0.0046 7.556 7.559
0.0025 7.582 7.586
0.0015 7.603 7.603
0.0008 7.617 7.613
Table S3. Experimental concentrations and chemical shifts (dexp) of 2-mon-oct from variable
concentration 1H NMR (500 MHz, C6D6) compared to predicted chemical shifts (dp) from the
monomer–dimer equilibrium model.

dmon (ppm) ddim (ppm) Keq DG˚ (kcal/mol) s

7.628 6.987 14.82 -1.60 0.0039
Table S4. Optimal monomer–dimer model values to minimize standard deviation between
experimental and predicted values for 2-mon-oct.

Concentration (M) dexp (ppm) dp (ppm)

0.0673 7.320 7.320
0.0495 7.336 7.334
0.0330 7.349 7.349
0.0233 7.358 7.358
0.0168 7.362 7.365
0.0095 7.370 7.373
0.0053 7.373 7.377
0.0031 7.374 7.380
0.0017 7.376 7.381
Table S5. Experimental concentrations and chemical shifts (dexp) of 3-mon-oct from variable
concentration 1H NMR (500 MHz, C6D6) compared to predicted chemical shifts (dp) from the
monomer–dimer equilibrium model.

dmon (ppm) ddim (ppm) Keq DG˚ (kcal/mol) s

7.384 6.788 1.002 -0.0012 0.0037
Table S6. Optimal monomer–dimer model values to minimize standard deviation between
experimental and predicted values for 3-mon-oct.

S13
In-Depth Topological Discussion of Perplexanes

In claiming to require a new topological descriptor for the synthesized perplexanes, it is important
to highlight why existing descriptors do not adequately describe these structures.

First, this issue is complicated by the existence of two different but often conflated topological
formalisms: mathematical topology and chemical topology. This friction arises for two reasons.
The first is because there are many objects whose topologies are mathematically trivial (i.e. not
meaningfully distinct), yet as molecules they display distinct properties and structures that are
important to describe and catalog. An illustrative example is the rotaxane, a structure in which a
circle is threaded by a linear axle, which cannot be dethreaded due to the presence of bulky
stoppers. In mathematics, this structure is topologically meaningless; the size of the circle is not
defined by the topology, and thus if the circle is large enough it can always dethread. Yet in
chemistry this motif effectively interlocks two molecular components, and it is a valuable endeavor
to understand how different imposed topologies affect the properties of rotaxanes. The second is
because mathematical topology is well developed to discuss certain types of topological
complexity (particularly knotting and braiding) but does not contain good descriptive
nomenclature for a large swathe of potential entangled structures. Thus, there are some instances
for which the types of molecules accessible to chemists are not easily described by existing
mathematical topology. In these cases, chemists often develop colloquial names that are more
facile for describing new structures within the community. Catenanes are good examples of this,
in that they are mathematically links, but the wide range of linking patterns for even a handful
simple rings are not simply delineated by existing nomenclature. Chemists often find it easier to
catalog molecular links using the [n]catenane nomenclature, where “n” denotes the number of
interlocked components, and simple additional descriptions, such as “radial”, “linear”, or
“branched” catalog different linking patterns.10 Thus, when we discuss a new topological class, it
is important to distinguish between its mathematical descriptors, which provide a crucial
theoretical framework for thinking about topology, and its chemical descriptors, which catalog
important structural features in a way that facilitates better chemical understanding.

For the proposed perplexanes, we make the case that they do not fit into existing mathematical
descriptions of knots or links yet contain mathematically non-trivial features, and further, that
although the family is connected by an obvious and intuitive structural motif, different members
of the family contain distinct underlying topological features. Due to the absence of an existing
mathematically rigorous name, and to the structural similarity of this family despite subtly
different underlying topologies, we feel that the development of a new chemical topology
descriptor is the most useful way to classify these molecules. Below, evidence for these claims is
presented.

First, the existence of branching points (in this case tripodal vertices) formally precludes these
structures from being knots or links, even if they may contain these elements. This is because the

S14
formal definition of a knot is “the embedding of a circle in three-dimensional Euclidean space”,
meaning they must consist of a single closed loop. Branched, entangled structures are broadly
defined in mathematics as knotted graphs, but this area is relatively unexplored, and in its current
form not suited to systematic cataloging of entangled structures. One subclass in this family,
Ravels, were formally developed in 2008,11 and experimentally realized in molecules in 2019.7
Ravels, however, are not global topological features as is the case for knots and links, but are
localized around vertices. In ravels, each arm of a given vertex entangles the other arms, as
illustrated effectively in reference 11. The topological features of perplexanes are not localized
around their vertices, confirming that they are not Ravels.

The mathematically non-trivial features of perplexanes consist of the larger features of the parent
knot or link, in addition to the rotaxane-like interlocking of the additional introduced cycles.
Unlike in rotaxanes, however, this interlocking is topologically non-trivial because it can only be
disentangled by breaking the cycle. Because of this, link-derived perplexanes (e.g. Hopf and
Solomon) contain two distinct modes of interlocking, while knot-derived perplexanes (e.g. trefoil
and pentafoil) contain both interlocking and interweaving motifs.

From this line of reasoning, it is clear that perplexanes contain a unique set of topological features
not previously observed in either mathematics or chemistry. Their simple derivation from classical
topological knots and links makes them objects of interest for further chemical investigation,
warranting their identification as a new topological class.

S15
 1

9
7.56
7.56
143.80

7.8
7.55
7.54

140
7.54

7.7
134.49
7.54
132.64

8
7.48
128.31
7.47

7.6
125.65
2.01 7.47
125.55
2.02 7.46
123.74

7.5
1.04 7.46
122.27
7.46

120
0.95

7
1.00 7.33

7.4
7.33
7.33
7.33

f1 (ppm)
7.3
7.31
105.39
7.31

7.2

6
7.30

100
7.30
7.26 CDCl3

7.1
94.77
7.09
7.09
7.0 7.08
7.08

5
1.45
6.9

1.45

80
77.37 CDCl3
1.44
H, 13C{1H}, and Selected 2D NMR spectra

77.16 CDCl3
76.95 CDCl3 1.44
1.44
1.43

4
1.43

f1 (ppm)

f1 (ppm)
1.42
1.42

60
1.42
1.42
1.41

Figure S3. 1H NMR Spectrum (400 MHz, CDCl3) of S4.

1.41
1.41
1.41
1.40

Figure S4. 13C{1H} NMR Spectrum (151 MHz, CDCl3) of S4.

1.40

40
1.39
2
f1 (ppm)

0.94
0.93
0.92
26.40 4.25 0.92
26.20 0.92
0.72
1

3.16 0.72

20
2.13 0.72
16.06
0.72
1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5

13.96
0.71
6.35 0.71
0.71
0

0.70
0.70

0
0.70
-1.53
0.24
0.23
0.23
-1

0.08

S16
 160
143.80

140
134.49
132.64
143.79 128.31
125.65

140
134.48 125.55
132.63 123.74
128.29 122.27

120
125.63
125.53
123.72
122.27

120
105.39

100
105.42
94.77

100
94.79

80
77.37 CDCl3
77.16 CDCl3
77.37 CDCl3 76.95 CDCl3

80
77.16 CDCl3
76.95 CDCl3

f1 (ppm)
f1 (ppm)
60

Figure S5. 1H NMR Spectrum (400 MHz, C6D6) of S5.

60

Figure S6. 13C{1H} NMR Spectrum (151 MHz, C6D6) of S5.

40

40
33.43
32.10
29.48
29.43 26.40
23.99 26.20
23.95

20
22.85
20

16.33
16.06
14.27
13.96

0
-1.51
0

-1.53

S17
 7.26 CDCl3
7.26 cdcl3

1.54 H2O
8.80
8.78

7.84
7.82
7.62
7.60
7.51
7.49
7.48
7.47
7.38
7.37

1.45
1.44
1.43
1.42
1.38
0.95
0.93
0.92
0.74
0.72
0.70
0.24
9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2
1H NMR (ppm)

1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
1H NMR (ppm)
2.08

2.06
2.07

1.06
1.00

4.27

3.10

2.07

6.12
2.11

9.5 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 -0.5
1H NMR (ppm)

Figure S7. 1H NMR Spectrum (400 MHz, C6D6) of 2-mon.

77.37 CDCl3
77.16 CDCl3
76.95 CDCl3
170.21

143.55
143.38
137.41
134.96
134.09
132.61
129.34
125.22
125.14
124.98
124.74
122.33

105.49

94.99

26.45
26.25

14.02
16.11

-1.44

180 160 140 120 100 80 60 40 20 0

f1 (ppm)

Figure S8. 13C{1H} NMR Spectrum (151 MHz, THF-d8) of 2-mon.

S18
 7.26 CDCl3

1.54 H2O
7.77
7.61
7.61
7.60
7.59
7.51
7.50
7.49
7.49
7.48
7.43
7.42
7.37
7.36

0.27
7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2
f1 (ppm)
1.00
2.05
2.09
1.08
1.09

9.19
8 7 6 5 4 3 2 1 0
f1 (ppm)

Figure S9. 1H NMR Spectrum (400 MHz, C6D6) of 3-mon.

143.65
143.24

135.69
134.20
132.71
125.41
125.09
124.76
122.42
122.16

105.00

95.63

77.37
77.16
76.95

0.13

145 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5
f1 (ppm)

Figure S10. 13C{1H} NMR Spectrum (151 MHz, THF-d8) of 3-mon.

S19
 7.26 CDCl3
8.69
8.68

7.65
7.64

1.54
1.46
1.39
1.31

0.89
0.72

0.27
8.7 8.5 8.3 8.1 7.9 7.7 7.5 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
1H NMR (ppm) 1H NMR (ppm)

6.00 5.93 6.14 6.38 24.80 9.23 6.01 17.69

9.5 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 -0.5
1H NMR (ppm)

Figure S11. 1H NMR Spectrum (600 MHz, C6D6) of 1-mon-oct.

77.16 CDCl3
171.22

135.90
132.38
128.88
127.67

105.19

97.24

33.43

29.49
29.44
23.99
22.85
16.26
14.28
32.11

-1.57

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

13C NMR (ppm)

Figure S12. 13C{1H} NMR Spectrum (151 MHz, C6D6) of 1-mon-oct.

S20
 180
9
8.74
2.01 8.73
170.38
8.73
7.79
7.79

160
7.78

8
7.78
2.10
7.59
2.24
143.69 7.59
2.11
143.40 7.58
1.00
137.55 7.57
1.04
135.05 7.50

140
7
134.10 7.50
132.64 7.49
129.43 7.48
125.26 7.44
125.21 7.44
125.11 7.34

120
124.78 7.33
122.40 7.26 CDCl3

105.48

100
95.06

1.55 H2O

f1 (ppm)
f1 (ppm)
4
77.37 CDCl3 1.47

80
77.16 CDCl3 1.46
76.95 CDCl3 1.45
1.44
1.43
1.43
1.40

60
1.38
1.37
1.33
1.31

Figure S13. 1H NMR Spectrum (600 MHz, C6D6) of 2-mon-oct. 1.30

1.30
2

1.29

40
1.29
33.49

Figure S14. 13C{1H} NMR Spectrum (151 MHz, C6D6) of 2-mon-oct.

1.28
32.14
1.25
29.53 12.34 1.25
29.48
1.23
24.03
1

0.91
22.88 3.07

20
0.89
16.39 2.13 0.88
14.30 0.73
0.72
6.10 0.71
0

2.81 0.71
0.70

0
-1.43 0.25

S21
 7.57
7.54
143.29

8
7.54
143.09
7.53

140
7.52

7.7
135.30 1.03
7.49
134.11 2.16
7.49
132.64 1.96
7.48

7.6
125.25 1.05
7.48
124.80 1.00
7.47

7
124.58 7.26 CDCl3

7.5
122.38 7.25

120
121.55 7.24
7.22
7.21

7.4
f1 (ppm)

6
105.45

7.3

100
1.54
1.54

7.2
95.03
1.53
1.52
1.52

5
7.1
1.51
1.51
1.51 H2O

80
77.37 CDCl3
1.50
77.16 CDCl3
1.50
76.95 CDCl3
1.49
1.48

4
1.48

f1 (ppm)

f1 (ppm)
1.46
1.45
1.6

1.44

60
1.44
1.5

1.43
1.43
1.4

3
1.42
1.41
1.3

1.38
1.37
1.36

40
Figure S15. 1H NMR Spectrum (600 MHz, C6D6) of 3-mon-oct. 1.36
f1 (ppm)

33.46 1.36
1.36
2

32.12
1.2 1.1 1.0

29.51 1.35

Figure S16. 13C{1H} NMR Spectrum (151 MHz, C6D6) of 3-mon-oct.

29.46 1.35
0.9

24.01 1.35
22.86 1.33
11.98
0.8

1.33

20
1.33
16.36
0.7

14.29
3.17 0.95
0.94
0.6

2.15
0.93
0.92
2.80 0.78
6.18

0
0.77
-1.47 0.76
0

0.76
0.75
0.30

S22
 3.56 THF
3.52 THF

1.72 THF
1.67 THF

-0.35
8.25
8.24

6.91
6.89

6.40

2.40
8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4
1H NMR (ppm)

24.00 24.30 60.44 108.06

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 -0.5
1H NMR (ppm)

Figure S17. 1H NMR Spectrum (600 MHz, C6D6) of 1-Zr.

67.39 THF

25.31 THF
206.64

171.16

151.45
150.10

133.55
130.56
128.13

112.47

2.88

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
13C NMR (ppm)

Figure S18. 13C{1H} NMR Spectrum (151 MHz, C6D6) of 1-Zr.

S23
 1.4
9.0

10
3.97 7.53

7.6

8
2.05

1.2
7.53

8.5
2.31 7.52
2.22 7.52

7.4
1.0
1.75 7.51

8.0

9
2.04 7.49 1.99

7.2
0.8
2.10 7.47
2.16 7.47

7.5

7
6.01 7.46

7.0
f1 (ppm)
f1 (ppm)
2.27 7.45 12.00
3.88

7.0
7.42

8
2.76

0.6 0.4

6.8
2.04 7.41 4.01
3.89 7.41 22.09

0.2
6.5
1.81 7.36

6.6
177.91
8.89

f1 (ppm)
7.35
16.26

6
11.36

0.0
7.34
16.91
6.0

6.4
7
8.31 7.26
0.90 14.32
7.26

-0.2
20.18
7.24

6.2
21.53
7.24
74.31
7.15
5.94

6.0
7.15

6
6.34

5
7.13
4.61
7.12

5.8
7.11
7.11

5.6
7.09
7.08

5
7.08

4
7.05
7.04
7.01

f1 (ppm)
f1 (ppm)
6.99

4
6.99
6.95
6.95
6.94

3
6.93

Figure S20. 1H NMR Spectrum (600 MHz, C6D6) of 3-Zr.

Figure S19. 1H NMR Spectrum (600 MHz, C6D6) of 2-Zr.
6.87
6.87 3
6.86
6.86

0.25
6.85
6.82

2
6.74
2

0.15
6.73
6.67
6.65

0.05
6.65
6.65
1

f1 (ppm)
6.53

1
6.47

-0.05
3.62
3.62
3.62

-0.15
2.52 48.14
0

9.04 1.77 46.57

19.52 1.33

0
-0.25
9.12 0.14
19.42 -0.03
-0.07
-0.14
-1

S24
 7.26 CDCl3

-0.04
8.42
8.40

7.19
7.18

6.40

1.54
8.5 8.0 7.5 7.0 6.5
1H NMR (ppm)

24.00 23.39 11.81 107.48

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 -0.5
1H NMR (ppm)

Figure S21. 1H NMR Spectrum (600 MHz, C6D6) of 1.

170.43

160.67

146.05

134.50
132.19
129.70
127.99

77.16

0.47

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
13C NMR (ppm)

Figure S22. 13C{1H} NMR Spectrum (151 MHz, C6D6) of 1.

S25
 220
9

200
8
2.00

170
1.96

180
1.88
1.79
170.18
1.54

7
169.38
3.68

160
1.67
161.29

160
2.00
2.08
144.87
143.47 0.88

6
142.92 0.82

150
142.47

140
142.23
141.66

f1 (ppm)
137.73
137.00

5
134.90

120
134.29

140
133.12
8.0

132.75
131.31
131.17

100
129.36

4
f1 (ppm)

f1 (ppm)
7.5

129.10

130
128.97
128.60
125.47

Figure S23. 1H NMR Spectrum (600 MHz, C6D6) of 2.

7.0
f1 (ppm)

80
125.35
125.12

3
124.61
124.48

120

Figure S24. 13C{1H} NMR Spectrum (151 MHz, C6D6) of 2.

6.5

124.26
124.06

60
123.76
72.90
6.0

71.66
62.21
54.36 CD2Cl2

40
54.18 CD2Cl2 5.09
54.00 CD2Cl2 4.97
53.82 CD2Cl2
1

53.64 CD2Cl2 3.90

43.82 4.10

20
30.27 2.45
27.27 2.33
27.17
26.90 6.98
0

26.83 6.93

0
17.11
17.01
14.29
14.21
-1.02
-1.15

S26
 8.5

180
7.52
160.61 7.51

7.8
159.85 7.47

8.0
159.55 7.46

170
7.6

160
141.05 7.41
2.44
140.92

7.4
7.40
4.09

7.5
140.82 7.40

160
6.74

155
140.65

7.2
7.31
140.31 6.46
7.30
140.24 8.77

7.0
7.23

7.0

150
140.07 6.28

150
7.23
140.02 3.11

6.8
7.23
139.18 5.00
7.22

140
2.00

6.5
139.04

6.6
7.21

145
138.74 4.13
7.19
138.60

6.4
f1 (ppm)
1.00 7.19
132.15

130
7.11

6.0
132.09

140
6.2
1.00 7.10
131.98
7.10

f1 (ppm)
131.76

6.0

120
7.09
131.25 0.50

5.5

135
5.8 7.08
131.19
131.13 6.98
6.95

110
5.6

131.02

5.0
6.95

130
128.68
6.77
5.4

128.47
128.27 6.75

100
6.74
5.2

128.06

125
4.5
123.37 6.74
122.33 6.73

90
122.10 6.65

120
4.0
121.88 6.65

f1 (ppm)
f1 (ppm)
121.74 6.65

80
121.59 6.50

115
121.43 6.48

3.5
121.35 6.14

70
Figure S25. 1H NMR Spectrum (600 MHz, C6D6) of 3.
121.17 5.50
121.12
0.30

3.58

3.0
120.42 3.58

60
116.53 3.58

-1.0
116.03
0.25

3.58

Figure S26. 13C{1H} NMR Spectrum (151 MHz, C6D6) of 3.

65.05
1.73
2.5

-1.5
64.90

50
1.72
64.84
0.20

1.31
64.69
1.30
2.0

64.55

f1 (ppm)
1.29

40
64.40
0.15
f1 (ppm)

-2.0 -2.5
1.28
64.26
1.27
27.79

-3.0
1.5

0.90

30
22.93
0.10

22.80 0.89

-3.5
22.74 0.88
22.67 0.27
1.0

20
0.05

22.60 0.26
22.47 0.25
22.34 0.16
0.00

10
0.5

22.20 0.15
20.35 9.01 0.14
11.51 17.18 0.13

0
-1.85 26.46 0.13
0.0

-2.00 0.11
-2.09 0.09
-2.18 0.09

-10
-0.5

0.08

S27
MALDI-TOF Spectrometry

All MALDI-TOF spectrometry for 2 and 3 was conducted in positive mode using trans-2-[3-(4-
tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) as a matrix. The spectrum for
2 was acquired on an Applied Biosystems Voyager DE Pro in reflectron mode. 3 proved
significantly more difficult to ionize, and only a low resolution spectrum in linear mode was
achievable on the same instrument (Figure S28). The high resolution isotope pattern of 3 (Figure
S28, inset) was acquired on a Bruker Autoflex Max in reflectron mode.

1000

750
experimental

250
750
Intensity

-250
Intensity

simulated
500
-750
4795 4800 4805 4810 4815 4820
m/z

250

0
1000 1500 2000 2500 3000 3500 4000 4500 5000
m/z

Figure S27. MALDI-TOF spectra of 2 from 1000-5000 amu. Inset depicts the experimental
(black) and simulated (red) isotope pattern of 2.

S28
 1500
4000
experimental

2000

Intensity
0

1000
-2000

simulated
Intensity

-4000
5052 5062 5072 5082
m/z

500

0
1000 2000 3000 4000 5000 6000
m/z

Figure S28. MALDI-TOF spectra of 3 from 1000-6000 amu. Inset depicts the experimental
(black) and simulated (red) isotope pattern of 3.

S29
Absorption and Emission Spectroscopy

UV-Vis and fluorescence spectroscopies were performed on a Varian 5000 UV-Vis-NIR

spectrometer and Nanolog Spectrofluorimeter respectively using quartz cuvettes with a path length
of 1 cm. All UV-vis and fluorescence spectra were collected in DCM.

1.2
1-mon abs
1 1 abs
1-mon fluor
0.8
1 fluor
0.6

0.4

0.2

0
250 300 350 400 450 500 550 600
Figure S29. Normalized absorption (solid lines) and emission (dotted lines) for 1-mon (blue) and
1 (red) in DCM at 6.00x10-6 M and 2.91x10-6 M respectively.

1.2
2-mon abs
1 2 abs
0.8 2-mon fluor
2 fluor
0.6

0.4

0.2

0
250 300 350 400 450 500 550 600 650
Figure S30. Normalized absorption (solid lines) and emission (dotted lines) for 2-mon (blue) and
2 (red) in DCM at 3.17x10-5 M and 1.16x10-5 M respectively.

S30
 1.2
3-mon abs
1
3 abs
0.8 3-mon fluor
3 fluor
0.6

0.4

0.2

0
250 300 350 400 450 500 550 600 650
Figure S31. Normalized absorption (solid lines) and emission (dotted lines) for 3-mon (blue) and
3 (red) in DCM at 4.04x10-5 M and 1.30x10-5 M respectively.

X-ray Crystallography

Synchrotron data for 1-Zr, 2-Zr, and 3-Zr was collected on beamline 24-ID-C at the Advanced
Photon Source at a wavelength of 0.7749 Å, Argonne National Laboratory, which is equipped with
a single axis MD2 goniometer, X-ray diffractometer and a Dectris Eiger2 16M pixel array detector
at a distance of 150 mm. This single axis goniometer limited our achievable value of sin(theta-
max)/wavelength but did not affect the unambiguous determination of this structure. All diffraction
data were processed using the XDS suite of programs.12 All structures were solved ab initio using
direct methods in SHELXT.13-14 Olex2 software was used for the refinement.15

Crystals of 1Zr were found to be uniformly weakly diffracting, exhibiting little diffraction beyond
0.90 Å. Positional disorder is present in two of the zirconocene “vertices” of the molecule; this
was modeled with use of the AFIX 55 constraint and fixed 50% occupancies of the two disordered
components. Additionally, these vertex units displayed varying extents of disorder within the bis-
trimethylsilylzirconacyclopentadienyl moieties; this disorder was modeled in two positions using
fixed 50% occupancies. To maintain reasonable anisotropic displacement parameters within the
disordered moieties, RIGU, EADP, and SIMU constraints / restraints were used. The asymmetric
unit of 1Zr contains 5.5 molecules of benzene-d6 co-solvent which would be discreetly modeled;
an additional 0.67 molecules of benzene-d6 were modeled using a solvent mask. Hydrogen atoms
were added using a riding model and refined isotropically. Attempts to refine hydrogen atom
positions on atom C15 (part of a rotationally disordered trimethylsilyl group) using the appropriate
HFIX command did not lead to a converged refinement; thus, no hydrogen atoms have been placed
on atom C15.

For 2-Zr and 3-Zr, the non-hydrogen atoms were located in successive difference Fourier
syntheses and refined with anisotropic thermal parameters. All the hydrogen atoms were placed at

S31
the calculated positions and refined using a riding model with appropriate HFIX command. DISP
instructions were used for each scattering factor types. In case of 2-Zr, the data quality was very
poor. There were trapped solvent molecule which could not be modelled and were squeezed out
from the refinement model using solvent mask in Olex2. The data quality for 3-Zr was much
better, and most of the solvent benzene molecules in the structure could be modelled. The
remaining disordered solvent molecules were squeezed out. Rigid bond restraints such as DELU,
SIMU along with DFIX, DANG were used to stabilize the structure in both the cases especially in
the case of hanging butyl chain in 2-Zr.

Identification code 1-Zr

Empirical formula C241.02D37.02H213N12Si12Zr6
Formula weight 4236.42
Temperature/K 273.15
Crystal system monoclinic
Space group C2/c
a/Å 63.908(6)
b/Å 23.962(2)
c/Å 35.276(3)
α/° 90
β/° 94.193(4)
γ/° 90
Volume/Å3 53876(9)
Z 8
μ/mm-1 0.344
F(000) 17505.0
Crystal size/mm3 0.11 × 0.1 × 0.06
synchrotron
Radiation
(λ = 0.7288)
2Θ range for data collection/° 2.182 to 48.004
–71 ≤ h ≤ 71,
Index ranges –26 ≤ k ≤ 26,
–39 ≤ l ≤ 39
Reflections collected 243662
38943
Independent reflections [Rint = 0.0512,
Rsigma = 0.0352]
Data/restraints/parameters 38943/445/2626
Goodness-of-fit on F2 1.423
R1 = 0.0875,
Final R indexes [I>=2σ (I)]
wR2 = 0.3001
R1 = 0.1028,
Final R indexes [all data]
wR2 = 0.3176
Largest diff. peak/hole / e Å–3 1.09/–1.84

S32
Table S7. Crystal data and structure refinement for 1-Zr.

Identification code 2-Zr

Empirical formula C360 H372 N12 S12 Si12 Zr6 [+ solvent]
Formula weight 6135.84
Temperature/K 100
Crystal system Monoclinic
Space group P 21/c
a/Å 13.820(3)
b/Å 46.380(9)
c/Å 69.940(14)
α/° 90
β/° 93.745(19)
γ/° 90
3
Volume/Å 44734 (16)
Z 4
3
ρcalcg/cm 0.911
-1
μ/mm 0.622
F(000) 12864
3
Crystal size/mm 0.210×0.190×0.015
Radiation Synchrotron (λ = 0.97918)
2Θ range for data collection/° 0.73 to 25.19
Index ranges -11 ≤ h ≤ 10, -37 ≤ k ≤ 39, -58 ≤ l ≤ 53
Reflections collected 77563
Independent reflections 27515
Data/restraints/parameters 27515/5861/2797
2
Goodness-of-fit on F 1.369
Final R indexes [I>=2σ (I)] R1 = 0.1393, wR2 = 0.3894
Final R indexes [all data] R1 = 0.1726, wR2 = 0.4169
-3
Largest diff. peak/hole / e Å 0.63/-0.43
Table S8. Crystal data and structure refinement for 2-Zr.

Identification code 3-Zr

Empirical formula C942 H906 S36 Si36 Zr18 [+ solvent]
Formula weight 16033.79
Temperature/K 100
Crystal system trigonal
Space group P 31
a/Å 41.640(8)
b/Å 41.640(8)
c/Å 58.480(12)

S33
 α/° 90.00(3)
β/° 90.00(3)
γ/° 120.00(3)
3
Volume/Å 87813 (38)
Z 3
3
ρcalcg/cm 0.910
-1
μ/mm 2.329
F(000) 25074
3
Crystal size/mm 0.195×0.050×0.010
Radiation Synchrotron (λ = 1.5000)
2Θ range for data collection/° 1.40 to 52.22
Index ranges -42 ≤ h ≤ 42, -43 ≤ k ≤ 43, -61 ≤ l ≤ 61
Reflections collected 697469
Independent reflections 142827
Data/restraints/parameters 142827/12548/7526
2
Goodness-of-fit on F 0.997
Final R indexes [I>=2σ (I)] R1 = 0.0810, wR2 = 0.2227
Final R indexes [all data] R1 = 0.0875, wR2 = 0.2318
-3
Largest diff. peak/hole / e Å 1.06/-0.37
Flack parameter 0.433 (7)
Table S9. Crystal data and structure refinement for 3-Zr.

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