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NATURE CHEMISTRY | www.nature.com/naturechemistry 1
SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S1
Discovery and introduction of a (3,18)-connected net
as an ideal blueprint for the design of metal–organic frameworks
Vincent Guillerm,1 Łukasz J. Weseliński,1 Youssef Belmabkhout,1 Amy J. Cairns,1 Valerio D’Elia,2 Łukasz Wojtas,3 Karim Adil,1 and Mohamed Eddaoudi1* 1Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 2Kaust Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 3Department of Chemistry, University of South Florida, 4202 East Fowler Ave., Tampa, Florida, 33620, United States of America. *e-mail: [email protected]
Supplementary Information
S1
Discovery and introduction of a (3,18)-connected net
as an ideal blueprint for the design of metal–organic frameworks
Vincent Guillerm,1 Łukasz J. Weseliński,1 Youssef Belmabkhout,1 Amy J. Cairns,1 Valerio D’Elia,2 Łukasz Wojtas,3 Karim Adil,1 and Mohamed Eddaoudi1* 1Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 2Kaust Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 3Department of Chemistry, University of South Florida, 4202 East Fowler Ave., Tampa, Florida, 33620, United States of America. *e-mail: [email protected]
Supplementary Information
S1
Discovery and introduction of a (3,18)-connected net
as an ideal blueprint for the design of metal–organic frameworks
Vincent Guillerm,1 Łukasz J. Weseliński,1 Youssef Belmabkhout,1 Amy J. Cairns,1 Valerio D’Elia,2 Łukasz Wojtas,3 Karim Adil,1 and Mohamed Eddaoudi1* 1Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 2Kaust Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 3Department of Chemistry, University of South Florida, 4202 East Fowler Ave., Tampa, Florida, 33620, United States of America. *e-mail: [email protected]
Supplementary Information
S1
Discovery and introduction of a (3,18)-connected net
as an ideal blueprint for the design of MOFs
Vincent Guillerm,1 Łukasz J. Weseliński,1 Youssef Belmabkhout,1 Amy J. Cairns,1 Valerio D’Elia,2 Łukasz Wojtas,3 Karim Adil,1 and Mohamed Eddaoudi1* 1Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 2Kaust Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 3Department of Chemistry, University of South Florida, 4202 East Fowler Ave., Tampa, Florida, 33620, United States of America. *e-mail: [email protected]
Supplementary Information
© 2014 Macmillan Publishers Limited. All rights reserved.
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S2
Table of Content
Materials and Methods………………………………………………...………….S3
Thermal stability…………………………………………………………………S28
Spectroscopy……………………………………………………………...……..S31
Topological analysis……………………………………………………………..S33
Structural details…………………………………………………...…………….S55
Gas sorption experiments………………………………………………………..S61
Catalysis studies………………………………………………………………....S67
Bibliography……………………………………………………………………..S71
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S3
Materials and Methods
Instrumentation
Powder X-ray Diffraction (PXRD) measurements were carried out at room temperature on a
PANalytical X’Pert PRO diffractometer 45kV, 40mA for CuKα (λ = 1.5418 Å) with a scan
speed of 0.02o.min-1 and a step size of 0.008o in 2θ.
Variable temperature Powder X-ray Diffraction (VT-PXRD) measurements were carried out
under primary vacuum in an Anton-Parr High temperature chamber attached to a PANalytical
X’Pert PRO diffractometer 45kV, 40mA for CuKα (λ = 1.5418 Å). Heating rate 5oC.min-1.
Optical microscopy was performed using a Shchfang CCM-55E microscope (magnification
x100) coupled to a computer interface through a JVC image recorder.
High-resolution dynamic thermogravimetric analysis (TGA) measurements were performed
on a TA Q500 apparatus, under nitrogen atmosphere (flow = 25 cm3.min-l).
Fourier-transform Infrared (FT-IR) spectra (4000 – 600 cm-1) were recorded on a Thermo
Scientific Nicolet 6700 apparatus. The peak intensities are described in each of the spectra as
very strong (vs), strong (s), medium (m), weak (w) and broad (br).
X-ray Single Crystal Diffraction data were collected using Bruker X8 PROSPECTOR APEX2
CCD diffractometer using CuKα (λ = 1.54178 Å). Indexing was performed using APEX2
(Difference Vectors method).1 Data integration and reduction were performed using SaintPlus
6.01.2 Absorption correction was performed by multi-scan method implemented in SADABS.3
Space group was determined using XPREP implemented in APEX2.1 Structure was solved using
Direct Methods (SHELXS-97) and refined using SHELXL-97 (full-matrix least-squares on F2)
contained WinGX v1.70.014-6 and OLEX2 programs packages.7
In case of gea-MOF-1, the ligand is disordered over two positions and all atoms (except metal
cations) have been refined isotropically and using distance (DFIX, SADI) and planarity (FLAT)
restraints. Hydrogen atoms were placed in geometrically calculated positions and included in the
refinement process using riding model with isotropic thermal parameters: Uiso(H) = 1.2Ueq(-CH).
The contribution of heavily disordered counterions and solvent molecules was treated as diffuse
using Squeeze procedure implemented in Platon program.8,9
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S4
In case of Tb-hexanuclear cluster cluster, refinement of disordered structure revealed that there
are only 11 ligand anions coordinated to the cluster. The vacant coordination sites are occupied
by one DMF and one NO3- coordinated to Tb2. This possibility has been confirmed through CSD
search revealing the analogical non-disordered structure with some of ligands substituted by
DMF/NO3- (Refcode: FUZBEI).10 The refinement of disordered structure has been carried using
geometry restraints and AFIX 66 constraints. No restraints for ADPs have been used. Majority of
disordered atoms have been refined isotropically. The cluster is negatively charged and the
structure is charge balanced most likely by [NH2(CH3)22+] cations. Due to the disorder it was not
possible to locate counterions but there is accessible volume of 153Å3 per unit cell where those
disordered cations could be located.
The crystal of gea-MOF-2 diffracted only up to 1.4Å resolution so the restraints have been used
to keep the model chemically feasible. Conformation of ligand has not been restrained. The
ligand is disorder over at least two major positions with approximate 1:1 occupancy ratio. The
disorder is most likely continuous so in order to better describe the electron density most of the
displaced parameters have been refined anisotropically and with RIGU/SIMU restraints. The
contribution of HIGHLY disordered solvent molecules was treated as diffuse using SQUEEZE
procedure implemented in the PLATON program.8,9
Crystal data and refinement conditions are presented in Supplementary Table 1-3.
The theoretical surface area of gea-MOF-1 was estimated using a Monte Carlo algorithm using
a previously reported strategy.11 The following diameters of each atom constituting the gea-
MOF-1 were taken from the UFF force field:12 C (3.43 Å), O (3.12 Å), H (2.57 Å), Y (2.98 Å).
The diameter of the nitrogen probe was considered to be 3.60 Å.13 Theoretical pore volume was
calculated using Materials Studio (Accelrys software).
Low-pressure gas sorption measurements were performed on a fully automated Quadrasorb SI
(for N2 sorption screening) and Autosorb-iQ gas adsorption analyzer, (Quantachrome
Instruments) at relative pressures up to 1 atm. The cryogenic temperatures were controlled using
liquid nitrogen and argon baths at 77 K and 87 K, respectively. The bath temperature for the CO2
sorption measurements was controlled using an ethylene glycol/H2O re-circulating bath.
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S5
High pressure adsorption isotherms of CO2, CH4 , N2, H2, C2H6, C3H8 and n-C4H10:
Adsorption equilibrium measurements of pure gases were performed using a Rubotherm
gravimetric-densimetric apparatus (Bochum, Germany) (Supplementary Scheme 1), composed
mainly of a magnetic suspension balance (MSB) and a network of valves, mass flowmeters and
temperature and pressure sensors. The MSB overcomes the disadvantages of other commercially
available gravimetric instruments by separating the sensitive microbalance from the sample and
the measuring atmosphere and is able to perform adsorption measurements across a wide
pressure range, i.e. from 0 to 20 MPa. The adsorption temperature may also be controlled within
the range of 77 K to 423 K. In a typical adsorption experiment, the adsorbent is precisely
weighed and placed in a basket suspended by a permanent magnet through an electromagnet.
The cell in which the basket is housed is then closed and vacuum or high pressure is applied. The
gravimetric method allows the direct measurement of the reduced gas adsorbed amount .
Correction for the buoyancy effect is required to determine the excess and absolute adsorbed
amount using equation 1 and 2, where Vadsorbent and Vss and Vadorbed phase refer to the volume of the
adsorbent, the volume of the suspension system and the volume of the adsorbed phase,
respectively.
)( phaseadsorbedssadsorbentgasabsolute VVVm (1)
)( ssadsorbentgasexcess VVm (2)
The buoyancy effect resulted from the adsorbed phase maybe taken into account via correlation
with the pore volume or with the theoritical density of the sample.
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S6
Supplementary Scheme 1. Representation of the Rubotherm gravimetric-densimetric apparatus.
These volumes are determined using the helium isotherm method by assuming that helium
penetrates in all open pores of the materials without being adsorbed. The density of the gas is
determined using Refprop equation of state (EOS) database and checked experimentally using a
volume-calibrated titanium cylinder. By weighing this calibrated volume in the gas atmosphere,
the local density of the gas is also determined. Simultaneous measurement of adsorption capacity
and gas phase density as a function of pressure and temperature is therefore possible.
The pressure is measured using two Drucks high pressure transmitters ranging from 0.5 to 34 bar
and 1 to 200 bar, respectively, and one low pressure transmitter ranging from 0 to 1 bar. Prior to
each adsorption experiment, about 200 mg of sample is outgassed at 473 K at a residual pressure
10-6 mbar. The temperature during adsorption measurements is held constant by using a
thermostated circulating fluid.
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S7
Toth Model for single gas adsorption fitting: In the current work, the Toth model was used to
fit the pure gas isotherms because of its suitable behavior at both low and high pressure and its
simple formulation as expressed by equation 3.14
mms
KP
KPnn 1))(1(
(3)
where n is the amount adsorbed, ns is the amount adsorbed at saturation, P is the equilibrium
pressure, K is the equilibrium constant, and m is a parameter indicating the heterogeneity of the
adsorbent.
Prediction of multicomponent gas adsorption Ideal Adsorption Solution Theory (IAST):
The Ideal Adsorption Solution Theory (IAST) proposed by Mayer and Prausnitz15 uses pure
gases adsorption isotherms to predict the mixture adsorption equilibrium at the temperature of
interest. For IAST application, the main condition to be fulfilled is the availability of (i) good
quality single component adsorption data of different gases, and (ii) excellent curve fitting model
for such data.16,17 In the current work, MSL and DSL models was used to fit the pure gas
isotherms as mentioned earlier
The most important equations used in the IAST calculation are listed hereafter:
)(0 iii fxf (4)
0
0lnif
ii fdnRT
A (5)
i i
i
t nx
n 0
1 (6)
iCO
iCOiCO yy
xxS
//
2
2
2 (7)
where if is the fugacity of component i in the gas phase; 0if is the standard-state fugacity, i.e.
the fugacity of pure component i at the equilibrium spreading pressure of the mixture, ; ix and
iy are the mole fractions of component i in the adsorbed and gas phase, respectively; A is the
surface area of the adsorbent, in is the number of moles adsorbed of pure component i (i.e., the
pure-component isotherm), and 0in is the number of moles adsorbed of pure component i at the
standard-state pressure
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S8
Equation 4 is the central equation of IAST, specifying the equality of the chemical potential of
component i in the gas and the adsorbed phase (which is assumed to be ideal in the sense of
Raoult’s law). Equation 5 allows the calculation of the spreading pressure from the pure-
component adsorption isotherm. The total amount adsorbed of the mixture, tn and the selectivity
of CO2 with respect to i, iCOS 2 are given by equations 6 and 7, respectively. The selectivity
iCOS 2 reflects the efficiency of CO2 separation.
1H NMR and 13C NMR spectra were recorded on a Bruker Advance III 400, 500, 600 and 700
MHz, chemical shifts for 1H NMR spectra are reported in ppm (δ, relative to TMS) using CHCl3
residual peak (δ = 7.26 ppm) in CDCl3 or DMSO ( = 2.50 ppm) in DMSO-d6 as an internal
standard, and for 13C NMR spectra solvent peaks at 77.16 and 2.50 ppm, respectively.
Elemental analysis was performed using a ThermoFinnigan Apparatus.
Calcination was performed under air atmosphere in a preheated Thermolyne (Thermo
Scientific) furnace.
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S9
Experimental Methods
All chemicals and solvents were used as received unless otherwise stated. Distilled water (H2O) is
obtained from Milli-Q (Millipore apparatus). Epoxides, Sigma Aldrich, variable purities, were stirred for
at least 6 h over CaH2 before distillation. Tetra-n-butylammonium bromide (TBAB), Sigma Aldrich,
99.0 %, was molten at 100-150 °C in a Schlenk tube, stirred under vacuum for 6 hours and stored under
argon atmosphere. N,N-Dimethylformamide (DMF, dried for ligand synthesis only) and toluene, 99%,
Fisher Scientific or Sigma Aldrich, were dried over CaH2. Tetrahydrofuran (THF), >99%, Sigma
Aldrich, was dried by distillation over LiAlH4. Potassium phosphate, >98%, Sigma Aldrich, was
thoroughly grounded using hot mortar and pestle.
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S10
Supplementary Scheme 2. Synthesis of the hexacarboxylate ligand L8 (H6L).
© 2014 Macmillan Publishers Limited. All rights reserved.
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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1982
S11
Preparation of dipropyl 9H-carbazole-3,6-dicarboxylate (L1): 9H-Carbazole-3,6-dicarboxylic acid18
(4.5 g, 17.6 mmol) was suspended in 1-propanol (110 mL), conc. H2SO4 (2 mL) was added and the
mixture was stirred at 110°C (oil bath) for 16 h. It was then cooled, concentrated on rotary evaporator
and taken in CH2Cl2 (200 mL). The organic layer was subsequently washed with aq. NaHCO3 (180 mL)
and dried over MgSO4. After filtration and removal of the solvent, cream solid was obtained in good
purity (5.4 g, 90%). MW=339. 1H NMR (600.1 MHz, CDCl3) δ = 8.9 (s, 2H), 8.7 (s, 1H), 8.2 (dd, J=1.4,
J=8.4, 2H), 7.5 (d, J=8.4, 2H), 4.4 (t, J=6.7, 4H), 1.9 (m, 4H), 1.1 (t, J=7.4, 6H). 13C NMR (150.9 MHz,
CDCl3) δ = 167.4, 142.9, 128.3, 123.3, 123.2, 122.8, 110.7, 66.7, 22.4, 10.8.
Preparation of dipropyl 9-(4-aminophenyl)carbazole-3,6-dicarboxylate (L2): Literature protocol was
adapted19: L1 (0.7 g, 2.1 mmol), 4-iodoaniline (0.45 g, 2.1 mmol), finely grounded K3PO4 (1.75 g, 8. 3
mmol), CuI (59 mg, 0.3 mmol), N,N’-dimethylethylenediamine (DMEDA) (0.14 mL), dry toluene (15
mL) were added to a Schlenk flask under argon atmosphere and heated at 110°C (oil bath) for 51 h.
After cooling, the mixture was partitioned between 2/1/1 EtOAc/std. NH4Cl/water (120 mL), organic
phase was separated, and then aqueous phase was further extracted with EtOAc (2 x 60 mL). Combined
organics were dried over Na2SO4. After filtration and removal of the solvent, the residue was subjected
to column chromatography (100% hexane to 50% AcOEt/hexane) to give off-white solid in sufficient
purity (0.72 g, 81 %). MW=430. Rf=0.2 (20% AcOEt/hexane). 1H NMR (500.1 MHz, CDCl3) δ = 8.9 (s,
2H), 8.1 (d, J=8.6, 2H), 7.3 (m, 4H), 7.0 (d, J=5.7, 2H), 4.8 (bs, 2H), 4.4 (t, J=6.6, 4H), 1.9 (m, 4H), 1.1
(t, J=7.4, 6H). 13C NMR (150.9 MHz, CDCl3) δ = 167.3, 144.8, 128.5, 128.2, 123.2, 123.1, 122.9, 122.8,
116.9, 109.9, 66.6, 22.4, 10.8.
Preparation of dipropyl 9-(4-iodophenyl)carbazole-3,6-dicarboxylate (L3): Literature protocol was
adapted20: BF3*Et2O (0.8 mL, 6.3 mmol) was dissolved in dry THF (5 mL) and cooled to -20°C
(acetone bath) under nitrogen. A solution of L2 (0.7 g, 1.6 mmol) in dry THF (12 mL) was added
dropwise for 5 minutes, followed by dropwise addition (10 min) of isopentyl nitrite (0.76 mL, 5.7 mmol)
in dry THF (10 mL). Formation of the solid was observed. The mixture was stirred for 45 min at the
same temperature, then allowed to warm to 0°C over 30 min. Anhydrous Et20 (30 mL) was added
dropwise, and the mixture was stirred at the same temperature for 5 minutes. The yellow solid (azonium
BF4 salt) was filtered and dried briefly at suction (1 g). The crude salt was suspended in CH3CN (35 mL)
and added to a solution of NaI (0.34 g, 2.3 mmol) in DI water (20 mL). After evolution of N2 subsided,
more DI water was added and the precipitate was filtered, washed with DI water, and dried at suction
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S12
briefly. The compound was further dried at high vacuum at 40°C overnight to yield cream solid in
sufficient purity (0.67 g, 76 %). MW=541. Rf=0.8 (20% AcOEt/hexane). 1H NMR (500.1 MHz, CDCl3)
δ = 8.9 (d, J=1.6, 2H), 8.2 (dd, J=1.6, J=8.6, 2H), 8.0 (d, J=8.5, 2H), 7.4 (d, J=8.6, 2H), 7.3 (d, J=8.5,
2H), 4.3 (t, J=6.7, 4H), 1.9 (m, 4H), 1.1 (t, J=7.4, 6H). 13C NMR (150.9 MHz, CDCl3) δ = 167.2, 143.9,
139.6, 136.3, 129.0, 128.4, 123.4, 123.3, 123.2, 109.7, 93.7, 66.7, 22.3, 10.8.
Preparation of 1,3-dibromo-5-ethynylbenzene (L4): General Sonogashira coupling procedure: a mixture
of dry toluene (20 mL)/triethylamine (5 mL) was degassed by bubbling argon through for 30 min. 1,3-
Dibromo-5-iodobenzene21 (1 g, 2.76 mmol), bis(triphenylphosphine)-palladium(II) chloride (116 mg,
0.166 mmol), CuI (53 mg, 0.276 mmol), followed by trimethylsilylacetylene (TMSA, 0.47 mL, 3.31
mmol) were added, and the mixture was stirred at 45°C for 16 h. After cooling, it was diluted with
CH2Cl2 (60 mL), washed with water (50 mL), then 1N HCl (50 mL), and dried with Na2SO4. After
filtration and removal of the solvent, the residue was chromatographed on silica using hexane as an
eluent. Slightly yellow liquid was obtained (0.86 g, 94%). According to 1H NMR, it contained up to
20% of 1-bromo-3,5-diethynylbenzene as an impurity.
The above mixture was dissolved in a mixture of MeOH (30 mL)/CH2Cl2 (15 mL) and Cs2CO3 (0.42 g,
1.3 mmol) was added, and then the mixture was stirred for 19 h at rt. 0.5 N HCl (40 mL)/CH2Cl2 (40
mL) was then added, phases separated, and then aqueous phase extracted again with CH2Cl2 (40 mL).
Combined organics were dried with Na2SO4. After filtration and removal of the solvent, the residue was
chromatographed on silica using hexane as an eluent. Less polar compound (first fraction) was separated
to give white solid (0.5 g, 69% in 2 steps). MW=260. NMR data were in agreement with previously
reported values.22
Preparation of dipropyl 9-{4-[(3,5-dibromophenyl)ethynyl]phenyl}-9H-carbazole-3,6-dicarboxylate
(L5): Using general Sonogashira coupling procedure as described for L4: to a degassed mixture of dry
toluene (20 mL)/triethylamine (5 mL), L3 (0.6 g, 1.1 mmol), L4 (0.29 g, 1.1 mmol),
bis(triphenylphosphine)palladium(II) chloride (47 mg, 0.067 mmol), and CuI (21 mg, 0.112 mmol) were
added, and the mixture was stirred at 50°C for 25 h. After cooling, it was diluted with CH2Cl2 (60 mL),
washed with water containing little ammonia (50 mL), then 1N HCl (50 mL), and dried with Na2SO4.
After filtration and removal of the solvent, the residue was chromatographed on silica using hexane to
70% CH2Cl2/hexane as an eluent. Light brown solid was obtained in sufficient purity (0.72 g, 96%).
MW=673. Rf=0.5 (60% CH2Cl2/hexane). 1H NMR (500.1 MHz, CDCl3) δ = 8.9 (s, 2H), 8.2 (d, J=8.8,
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S13
2H), 7.8 (d, J=7.9, 2H), 7.7 (m, 3H), 7.6 (d, J=8.0, 2H), 7.4 (d, J=8.6, 2H), 4.4 (t, J=6.6, 4H), 1.9 (m,
4H), 1.1 (t, J=7.4, 6H). 13C NMR (150.9 MHz, CDCl3) δ = 167.1, 143.9, 136.9, 133.7, 134.4, 133.2,
128.4, 127.1, 126.3, 123.5, 123.4, 123.2, 122.9, 122.5, 109.8, 90.8, 88.0, 66.7, 22.4, 10.8.
Preparation of dipropyl 9-{4-[(3,5-bis(trimethylsilylethynyl)phenyl)ethynyl]phenyl}-9H-carbazole-3,6-
dicarboxylate (L6): Using general Sonogashira coupling procedure as described for L4: to a degassed
mixture of dry toluene (20 mL)/triethylamine (5 mL), L5 (0.7 g, 1.04 mmol),
bis(triphenylphosphine)palladium(II) chloride (73 mg, 0.164 mmol), CuI (30 mg, 0.156 mmol) were
added, followed by trimethylsilylacetylene (TMSA) (0.34 mL, 2.4 mmol) and the mixture was stirred at
40°C for 25 h. After the same work-up as for L5, the residue was chromatographed on silica using
hexane to 10% AcOEt/hexane as an eluent. Less polar compound (first fraction) was separated to give
light yellow solid (0.505 g, 69%). MW=707. Rf=0.5 (60% CH2Cl2/hexane). 1H NMR (500.1 MHz,
CDCl3) δ = 8.9 (s, 2H), 8.2 (d, J=8.7, 2H), 7.8 (d, J=7.7, 2H), 7.62 (s, 2H), 7.6 (m, 3H), 7.4 (d, J=8.7,
2H), 4.4 (t, J=6.6, 4H), 1.9 (m, 4H), 1.1 (t, J=7.4, 6H). 13C NMR (150.9 MHz, CDCl3) δ = 167.2, 143.9,
136.6, 135.3, 134.8, 133.6, 128.4, 127.1, 124.0, 123.5, 123.41, 123.39, 123.2, 123.1, 109.8, 103.2, 96.1,
89.3, 66.7, 22.4, 10.8, 0.0.
Preparation of ligand (L8, H6L):
L6 (0.49 g, 0.69 mmol) was dissolved in a mixture of MeOH/CH2Cl2 (1/1, 20 mL), Cs2CO3 (0.23 g, 0.69
mmol) was added, and then the mixture was stirred for 11 h at rt. 0.5 N HCl (40 mL)/CH2Cl2 (40 mL)
was then added, phases separated, and then aqueous phase extracted again with CH2Cl2 (40 mL).
Combined organics were dried with Na2SO4. After filtration and removal of the solvent, the residue was
chromatographed on silica using hexane to AcOEt as an eluent, followed by CH2Cl2, to give 0.38 g of
white solid. Rf=0.9 (CH2Cl2). According to 1H NMR, a mixture of methyl/propyl esters in ca. 1/1 ratio
was obtained. 1H NMR (500.1 MHz, CDCl3), selected peaks: δ = 4.4 (t, J=6.6, OCH2-), 4.0 (s, OMe),
3.15 (s, 2H, CH), 1.9 (m, OCH2CH2-), 1.1 (t, J=7.4, -CH2CH3).
The above mixture of esters (0.37 g) was reacted with diethyl 5'-iodo-1,1':3',1''-terphenyl-4,4''-
dicarboxylate L723 (0.75 g, 1.5 mmol), bis(triphenylphosphine)palladium(II) chloride (58 mg, 0.082
mmol), CuI (26 mg, 0.137 mmol) in dry DMF (20 mL)/triethylamine (5 mL) at 50°C for 36 h using
general Sonogashira procedure as described for the synthesis of L4. After cooling, the mixture was
diluted with water (150 mL), filtered, and solid washed thoroughly with ethyl acetate. The filter cake
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was dissolved in CH2Cl2 (200 mL), washed with water containing ammonia (100 mL), then brine (100
mL), and dried with Na2SO4. After filtration and removal of solvent, the hexaester was obtained as a
yellow solid (0.716 g), which was taken into next step without further purification. Rf=0.5 (5%
MeOH/CH2Cl2).
The hexaester (0.716 g) was suspended in THF (50 mL)/MeOH (15 mL), solution of NaOH (0.5 g, 12.5
mmol) in H2O (20 mL) was added, and the mixture was stirred at 90°C for 12 h. After cooling, the
mixture was concentrated on rotary evaporator, diluted with water to 100 mL vol., filtered through
paper, and the filtrate was washed with AcOEt (50 mL). Then it was acidified with conc. HCl, and
centrifuged (6000 rpm, 3 min). Centrifugation was repeated 3x with DI water to neutral pH, then with 1x
acetone. Then the solid was suspended in acetone, concentrated on rotary evaporator and the residue was
further dried under high vacuum at 40°C overnight to yield brown solid in sufficient purity (0.47 g, 61
% in 3 steps). MW=1111, C72H41NO12. 1H NMR (700.1 MHz, DMSO-d6) δ = 13.0 (bs, 6H), 9.0 (s, 2H),
8.12 (m, 2H), 8.1 (m, 2H), 8.07 (d, J=8.3, 8H), 8.02 (d, J=1.4, 4H), 8.0 (d, J=8.3, 8H), 7.9 (m, 5H), 7.8
(d, J=8.3, 2H), 7.5 (d, J=8.6, 2H). 13C NMR (176 MHz, DMSO-d6) δ = 167.7, 167.2, 143.2, 143.0,
140.5, 136.4, 134.3, 133.6, 130.3, 130.0, 129.7, 128.4, 127.3, 126.6, 123.7, 123.6, 123.4, 123.1, 122.8,
121.7, 110.0, 90.8, 90.2, 88.6, 88.2.
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Supplementary Figure 1. 1H and 13C spectra of 9H-carbazole-3,6-dicarboxylic acid.
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Supplementary Figure 2. 1H and 13C spectra of L1.
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Supplementary Figure 3. 1H and 13C spectra of L2.
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Supplementary Figure 4. 1H and 13C spectra of L3.
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Supplementary Figure 5. 1H and 13C spectra of L4.
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Supplementary Figure 6. 1H and 13C spectra of L5.
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Supplementary Figure 7. 1H and 13C spectra of L6.
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Supplementary Figure 8.1H and 13C spectra of L8 (H6L).
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Preparation of (DMA+)2.[Y9(µ3-OH)8(µ2-OH)3((O2C–C6H4)3C6H3)6]n.(solv.)x, gea-MOF-1: A solution of
Y(NO3)3.6H2O (8.6 mg, 0.0225 mmol), H3BTB (6.6 mg, 0.015 mmol), 2-FBA (95.2 mg, 0.675 mmol),
DMF (2 mL) and H2O (0.5 mL) was prepared in a 20 mL scintillation vial and subsequently heated to
105oC for 36h in a preheated oven. The as-synthesized sample was purified through repeated washings
with DMF to yield small colorless rod shaped crystals (Supplementary Figure 9), which are stable and
insoluble in common organic solvents (Supplementary Figure 11). Crystals were harvested, soaked in
DMF overnight, and then exchanged in MeOH for one week. Note that the MeOH was refreshed at least
every 24h. (Yield: 4 mg, 40% based on yttrium). Elemental Analysis: C=48.68 % (theo: 49.38 %),
H=3.00% (3.19%), N=1.4% (0.48%)
Notes:
i. In the absence of 2-FBA, a previously reported MOF is isolated, i.e. Y-LOF (LOF:
Lanthanide-Organic Framework)(Supplementary Figure 10).24
ii. Same synthetic conditions can be applied using other rare earth nitrates (Eu, Tb, Er)
(Supplementary Figure 12)
Preparation of [Tb6(µ3-OH)8(O2C–C6H4F)11(DMF)(NO3-)(H2O)6], Tb hexanuclear-cluster: A solution
of Tb(NO3)3.5H2O (21.8 mg, 0.05 mmol), 2-FBA (56.4 mg, 0.4 mmol), DMF (2 mL) and H2O (0.5 mL)
was prepared in a 20 mL scintillation vial and subsequently heated to 105oC for 36h in a preheated oven.
The solution was then abandoned for slow evaporation at room temperature under air in a ventilated
fume hood. After approximately two months, few octahedral crystals were harvested.
Preparation of [(CuO)3(L8)]n.(solv)x, gea-MOF-2: A solution of Cu(BF4)2.2.5H2O (1.8 mg, 0.0078
mmol), H6L (1.6 mg, 0.0014 mmol), HNO3 (3.5M, 0.1 mL), DMF (1.5 mL) and EtOH (0.5 mL) was
prepared in a 20 mL scintillation vial and subsequently heated to 65oC for 7 days in a preheated oven.
The as-synthesized sample was purified through repeated washings with DMF to yield small blue
hexagonal shaped crystals, which are insoluble in common organic solvents. Crystals were harvested,
soaked in DMF overnight, and then exchanged in EtOH for one week. Note that the EtOH was refreshed
at least every 24h. Elemental Analysis: C=61.26 % (theo: 64.02 %,), H=3.64% (3.06%), N=2.73%
(1.04%)
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Supplementary Figure 9. Experimental and calculated powder X-ray diffraction (PXRD) patterns for gea-MOF-1, indicating the purity of the as-synthesized and MeOH exchanged samples. Insert: optical microscopy shows the hexagonal rod shape of the crystals of as-synthesized gea-MOF-1.
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Supplementary Figure 10. Experimental PXRD of the compound obtained without 2-FBA compared to calculated pattern for Ce-LOF.
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Supplementary Figure 11. Experimental PXRD pattern for gea-MOF-1 soaked in various organic solvents.
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Supplementary Figure 12. Experimental PXRD pattern for of gea-MOF-1 analogs obtained from other rare earth metals.
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Thermal stability
VT-PXRD Experiments
Supplementary Figure 13. VT-PXRD of gea-MOF-1_EtOH from 0C to 400C. Red lines are representative of each 100oC step. gea-MOF-1 retains its crystallinity up to the maximum reachable
temperature on the apparatus, i.e. 400oC.
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TGA Measurements
The as-synthesized gea-MOF-1 reveals a weight loss (32%) between 100 and 170oC and is
attributed to the removal of DMF and water from the pores of the framework. A second weight
loss (4%) at approximately 250oC can be attributed to the removal of strongly coordinated
species such as DMF or small amount of residual unreacted ligand. The third weight loss
between 550 and 600oC is assigned to the removal of the organic ligand due to degradation of the
structure.
The methanol exchanged gea-MOF-1 shows only two weight losses, i.e. the first is observed at
room temperature, attributed to the removal of methanol (12%) and the second loss, between 550
and 600oC is attributed –as for the as synthesized material- to the departure of the organic ligand
and the degradation of the structure.
Supplementary Figure 14. TGA of the as-synthesized (green) and the methanol exchanged (red) gea-MOF-1.
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The ethanol exchanged gea-MOF-2 sample shows two main weight losses, i.e. the first is
observed at room temperature, attributed to the departure of ethanol (28%) and the second loss,
between 250 and 300oC is attributed to the departure of the organic ligand and the degradation of
the structure. The continuous weight loss up to 700oC is then attributed to the continuous slow
combustion/oxidation of the degraded framework, due to the small amount of oxygen present.
Supplementary Figure 15. TGA of the ethanol exchanged gea-MOF-2.
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Spectroscopy
Infrared spectroscopy
The methanol exchanged gea-MOF-1 does not show any traces of DMF (C=O=1662 cm-1), nor non
coordinated ligand (C=O=1683 cm-1), and therefore confirms the quality of the solvent activation
procedure.
(cm-1) H3BTB: 1683 (s), 1605 (s), 1566 (m), 1511 (w), 1420 (m), 1391 (m), 1311 (m), 1279
(m), 1238 (m), 1177 (m), 1104 (m), 1013 (m), 887 (w), 844 (m), 763 (s), 696 (m).
(cm-1) As synthesized: 2927 (w), 2856 (w), 1662 (vs), 1608 (m), 1558 (w), 1499 (w), 1405 (s),
1381 (s), 1253 (m), 1183 (w), 1089 (s), 1062 (m), 1015 (w), 860 (m), 781 (s), 705 (w), 655 (s).
(cm-1) MeOH Exchanged: 3300 (br), 2941 (w), 2827 (w), 1584 (m), 1537 (m), 1405 (s), 1180
(w), 1105 (w), 1018 (s), 854 (m), 804 (w), 778 (s), 702 (m), 663 (w).
Supplementary Figure 16. FT-IR spectra for the as-synthesized (green) and MeOH exchanged (red) gea-MOF-1 compared to the H3-BTB ligand (black).
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The Ethanol exchanged gea-MOF-2 shows a very weak band (C=O=1651 cm-1) attributed to little traces
attributed to DMF, but uncoordinated ligand is absent (C=O=1684 cm-1).
(cm-1) H6L: 1684 (s), 1628 (w), 1596 (s), 1511 (m), 1475 (w), 1381 (w), 1368 (2), 1338 (2),
1229 (s), 1177 (m), 1106 (m), 1013 (m), 877 (w), 848 (m), 763 (s).
(cm-1) As synthesized: 1651 (vs), 1605 (s), 1566 (w), 1502 (2), 1475 (w), 1434 (w), 1381 (vs),
1285 (m), 1253 (m), 1229 (m), 1165 (m), 1091 (s), 1060 (m), 1024 (m), 985 (w), 916 (m), 843
(m), 781 (s).
(cm-1) EtOH Exchanged: 3300 (br), 1651 (w), 1598 (s), 1532 (m), 15467 (m), 1379 (s), 1361
(s), 1286 (s), 1250 (m), 1227 (m), 1164 (m), 1127 (m), 1109 (w), 1027 (m), 986 (w), 913 (w),
833 (m), 778 (s).
Supplementary Figure 17. FT-IR spectra for the as-synthesized (green) and EtOH exchanged (red) gea-MOF-2 compared to the H3L ligand (black).
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Topological analysis
Supplementary Figure 18. Relation between the hexa- and nonanuclear clusters, and effect of the cluster evolution on the resulting MBBs.
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gea-MOF-1
Supplementary Figure 19. Topological analysis of gea-MOF-1, a) each inorganic node (purple, representative of the inorganic cluster) is connected to 12 other inorganic nodes through 18 organic
nodes (green, representative of BTB ligand); b) view of the gea-net along c axis.
Prior to topological analysis, the structure has been simplified to its points of extension (Supplementary
Figure 8). The inorganic nonanuclear cluster is then reduced to an 18-connected node (α), while the
tritopic BTB ligand is reduced to a 3-connected node (β). gea-MOF-1 exhibits an unprecedented (3,18)-
connected topology:
Point symbol for net: {43}6{442.672.839}, (3,18)-c net with stoichiometry (3-c)6(18-c); 2-nodal net, new
topology; transitivity: [2344]
Topological terms for each node:
(α) Point symbol: {442.672.839}, Extended point symbol:
[4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.6(2).6(2).6(2).6(2).6(2).6
(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(4).6(4).6(4).
6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4)
.6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(10).6(10).6(10).6(10
).6(10).6(10).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(36).8(36).8(36).
8(36).8(36).8(36).8(36).8(36).8(36).8(36).8(36).8(36).8(16).8(16).8(16).8(16).8(16).8(16).8(32).8(32).8(
32).8(32).8(32).8(32).8(64).8(64).8(64)], Coordination sequence: 18 12 132 44 378 96 744 170 1242
264;
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(β) Point symbol: {43}, Extended point symbol: [4.4(3).4(3)], Coordination sequence: 3 44 22 214 63
514 124 934 207 1486.
Batten et al. reported recently a (3,18)-connected net with the Schläfli symbols (43)(439.666.848) that
can be simplified to the already known 4-connected uma topology.25 The topology we present here, with
the Schläfli symbols (43)6(442.672.839) cannot be reduced to any simpler net, and is therefore, to the best
of our knowledge, a novel and unpredicted (3,18)-connected MOF.
Supplementary Figure 20. Illustration of the pillaring of hxl layers in the gea-MOF-1, creating one-dimensional channels.
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Supplementary Figure 21. Hexagonal close packing of the MBBs in gea topology. For clarity, gea net is shown as an augmented net, gea-a.
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Supplementary Figure 22. Cubic close packing of the MBBs in rht topology. For clarity, rht net is shown as an augmented net, rht-a.
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Supplementary Figure 23. Comparison of rht and gea topologies: a) Inorganic MBB and main cages of gea-MOF-1, b) Main cages of gea-MOF-2, c) Main tiles of gea net, d) Main tiles of rht net, e)
Deconstruction of gea net, f) Deconstruction of rht net. For clarity, gea and rht net are shown as augmented nets.
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Supplementary Figure 24. Schematic representation of the different packing modes of the octahedral cavities in a) gea-MOF-1 and b) rht-MOFs. For clarity, gea and rht net are shown as
augmented nets.
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Supplementary Figure 25. Description of window and cavity size in cavity I (also described as channel) of gea-MOF-1. Note that in Supplementary Figures 25-27 the window shape is highlighted in
green.
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Supplementary Figure 26. Description of window and cavity size in the cavity II of gea-MOF-1.
Supplementary Figure 27. Description of window and cavity size in cavity III cage of gea-MOF-1.
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gea-MOF-2
Supplementary Figure 28. Topological analysis of gea-MOF-2, a) each 18-connected SBB (purple node) is connected to 12 other SBB through eighteen 3-connected nodes (green, center benzene of the ligand); b) view of the gea-MOF-2 along c axis. Topology is similar to gea-MOF-1. Point symbol
for net: {43}6{442.672.839}, (3,18)-c net with stoichiometry (3-c)6(18-c); 2-nodal net, new topology; transitivity: [2244]
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Supplementary Figure 29. a) Topological analysis of gea-MOF-2, described as a gwe net. The hexacarboxylate ligand is deconstructed into four 3-connected nodes, Cu paddle wheels are represented by a 4-connected node. Bottom part shows the augmented net, gwe-a. b) Correspondence between tiling
from gwe topology and cavities from gea-MOF-2. Point symbol for net: {6.82}6{62.82.102}{63.83}2{83}2, 3,3,3,4,4-c net with stoichiometry (3-c)2(3-c)2(3-c)4(4-c)2(4-c); 5-
nodal net, new topology; transitivity: [5575]
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Supplementary Figure 30. Topology of gea-MOF-2 can be described in several different ways, depending on the simplification of the Cu-nanoball and the ligand.
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gea-net
The structure has been simplified to its points of extension (Supplementary Figure 28). The
supermolecular building block (cage) is then reduced to an 18-connected node (α), while the central core
of the ligand is reduced to a 3-connected node (β). gea-MOF-2 exhibits the same (3,18)-connected
topology as gea-MOF-1:
Point symbol for net: {43}6{442.672.839}, (3,18)-c net with stoichiometry (3-c)6(18-c); 2-nodal net, new
topology; transitivity: [2244]
Topological terms for each node:
(α) Point symbol: {442.672.839}
Extended point symbol:
[4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.6(2).6(2).6(2).6(2).6(2).6
(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(4).6(4).6(4).
6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4)
.6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(10).6(10).6(10).6(10
).6(10).6(10).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(32).8(36).8(36).8(36).
8(36).8(36).8(36).8(36).8(36).8(36).8(36).8(36).8(36).8(16).8(16).8(16).8(16).8(16).8(16).8(32).8(32).8(
32).8(32).8(32).8(32).8(64).8(64).8(64)]
Coordination sequence: 18 12 132 44 378 96 744 170 1242 264
TD10: 3101
(β) Point symbol: {43}
Extended point symbol: [4.4(3).4(3)]
Coordination sequence: 3 44 22 214 63 514 124 934 207 1486
TD10: 3612
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gwe-net The structure has been simplified to its points of extension (Supplementary Figure 29). The
hexacarboxylate ligand is deconstructed into four 3-connected nodes, Cu paddle wheels are represented
by a 4-connected node:
Point symbol for net: {6.82}6{62.82.102}{63.83}2{83}2, 3,3,3,4,4-c net with stoichiometry (3-c)2(3-
c)2(3-c)4(4-c)2(4-c); 5-nodal net, new topology; transitivity: [5575]
Topological terms for each node: ______________________________________________ (a) Point symbol:{6.82} Extended point symbol:[6(2).8(3).8(3)] Coordination sequence: 3 6 18 25 43 59 93 104 182 179 TD10: 731 ______________________________________________ (b) Point symbol:{83} Extended point symbol:[8.8(3).8(3)] coordination sequence: 3 8 14 26 37 72 88 142 140 200 TD10: 713 ______________________________________________ (c) Point symbol:{6.82} Extended point symbol:[6.8.8(3)] Coordination sequence: 3 8 15 30 40 70 82 133 147 218 TD10: 747 ______________________________________________ (d) Point symbol:{63.83} Extended point symbol:[6.6.6.8(2).8(2).8(2)] Coordination sequence: 4 8 17 26 48 63 112 119 171 177 TD10: 746 ______________________________________________ (e) Point symbol:{62.82.102} Extended point symbol:[6.6.8(2).8(2).10(4).10(4)] Coordination sequence: 4 8 18 28 52 56 94 112 162 182 TD10: 717
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gwe-a-net Augmented gwe net
Point symbol for net: {3.12.13}3{3.162}3{4.12.14}2{4.122}, 3,3,3,3,3,3,3,3,3,3-c net with
stoichiometry (3-c)2(3-c)2(3-c)2(3-c)(3-c)2(3-c)2(3-c)2(3-c)2(3-c)2(3-c); 10-nodal net; New topology;
transitivity [ 10 17 12 5]
Topological terms for each node: ______________________________________________ (a) Point symbol:{3.162} Extended point symbol:[3.16.16(2)] Coordination sequence: 3 4 6 8 14 22 32 39 42 54 TD10: 225 ______________________________________________ (b) Point symbol:{3.12.13} Extended point symbol: [3.12(2).13(2)] Coordination sequence: 3 4 7 10 15 18 26 36 41 49 TD10: 210 ______________________________________________ (c) Point symbol: {3.162} Extended point symbol: [3.16.16(2)] Coordination sequence: 3 4 6 10 14 20 30 41 48 51 TD10: 228 ______________________________________________ (d) Point symbol:{3.162} Extended point symbol:[3.16(2).16(2)] Coordination sequence: 3 4 6 8 14 22 32 36 39 55 TD10: 220 ______________________________________________ (e) Point symbol:{3.12.13} Extended point symbol: [3.12.13] Coordination sequence: 3 4 7 10 15 19 29 41 48 59 TD10: 236 ______________________________________________ (f) Point symbol: {4.122} Extended point symbol: [4.12.12] Coordination sequence: 3 5 7 10 15 21 26 34 45 59 TD10: 226 ______________________________________________ (g) Point symbol: {3.12.13} Extended point symbol: [3.12.16(2)]
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Coordination sequence: 3 4 7 10 15 19 29 39 45 57 TD10: 229 ______________________________________________ (h) Point symbol:{4.12.14} Extended point symbol:[4.12.14] Coordination sequence: 3 5 7 10 15 22 28 34 47 63 TD10: 235 ______________________________________________ (i) Point symbol:{4.122} Extended point symbol:[4.12.12] Coordination sequence: 3 5 7 10 15 22 29 38 52 68 TD10: 250 ______________________________________________ (j) Point symbol: {3.162} Extended point symbol: [3.16(2).16(2)] Coordination sequence: 3 4 6 10 14 20 28 36 42 47 TD10: 211
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geb-net Point symbol for net: {42.63.8}{43.62.8}{43.63}, 4,4,4-c net with stoichiometry (4-c)(4-c)(4-c); 3-nodal
net, new topology; transitivity: [3774]
Topological terms for each node: ______________________________________________ (a) Point symbol:{43.62.8} Extended point symbol:[4.6.4.6.4.8(3)] Coordination sequence: 4 9 18 30 46 70 96 124 157 194 TD10: 749 ______________________________________________ (b) Point symbol:{43.63} Extended point symbol:[4.6.4.6.4.6] Coordination sequence: 4 9 16 27 44 66 92 121 154 191 TD10: 725 ______________________________________________ (c) Point symbol:{42.63.8} Extended point symbol:[4.6.4.6.6(2).8(3)] Coordination sequence: 4 10 20 34 52 72 95 127 167 208 TD10: 790
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gec-net Point symbol for net: {3.43.52.63.7}2{32.42.52.64}{63}, 3,5,5-c net with stoichiometry (3-c)(5-c)2(5-c); 3-
nodal net, new topology; transitivity: [3795]
Topological terms for each node: ______________________________________________ (a) Point symbol:{3.43.52.63.7} Extended point symbol:[3.4.4.4.5.6.6.6.5.7] Coordination sequence: 5 13 25 46 76 109 142 191 253 311 TD10: 1172 ______________________________________________ (b) Point symbol:{32.42.52.64} Extended point symbol:[3.3.4.4.6.6.6.6.5(2).5(2)] Coordination sequence: 5 12 23 44 77 109 139 185 251 310 TD10: 1156 ______________________________________________ (c) Point symbol:{63} Extended point symbol:[6.6(2).6(2)] Coordination sequence: 3 12 27 42 62 105 158 186 221 285 TD10: 1102
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ged-net Point symbol for net: {32.46.56.6}2{33.46.56}, 6,6-c net with stoichiometry (6-c)2(6-c); 2-nodal net, new
topology; transitivity: [2574]
Topological terms for each node: ______________________________________________ (a) Point symbol:{32.46.56.6} Extended point symbol:[3.3.4.4.4.4.4.4.5.5.6(3).5.5.5.5] Coordination sequence: 6 20 44 77 123 183 247 319 407 503 TD10: 1930 ______________________________________________ (b) Point symbol:{33.46.56} Extended point symbol:[3.3.3.4.4.4.4.4.4.5(2).5(2).5(2).5(2).5(2).5(2)] Coordination sequence: 6 18 42 78 122 174 244 324 400 490 TD10: 1899
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gea-a-net Augmented gea net
Point symbol for net: {3.43.52.83.9}2{3.82}3{32.42.52.84}, 3,3,5,5-c net with stoichiometry (3-c)(3-c)2(5-
c)2(5-c); 4-nodal net, new topology; transitivity: [4 9 10 5]
Topological terms for each node: ______________________________________________ (a) Point symbol:{3.43.52.83.9} Extended point symbol:[3.4.4.4.5.5.8.8.8.9] Coordination sequence: 5 13 22 33 53 86 126 157 183 226 TD10: 905 ______________________________________________ (b) Point symbol:{32.42.52.84} Extended point symbol:[3.3.4.4.5(2).5(2).8.8.8.8] Coordination sequence: 5 12 21 31 50 86 127 158 177 220 TD10: 888 ______________________________________________ (c) Point symbol:{3.82} Extended point symbol:[3.8(2).8(2)] Coordination sequence: 3 6 18 37 50 71 94 145 201 239 TD10: 865 ______________________________________________ (d) Point symbol:{3.82} Extended point symbol:[3.8.8(2)] Coordination sequence: 3 6 19 38 51 71 95 146 206 243 TD10: 879
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gez-net
The discovery of gea net led us to explore other possibilities to combine 18-connected nodes with 3-
connected nodes. We were indeed able to isolate a second (3,18)-connected net, named gez.
Ideal space group for gez net: R-3m.
Point symbol for net: {43}6{442.672.839}, (3,18)-c net with stoichiometry (3-c)6(18-c); 2-nodal net, new
topology; transitivity: [2232]
Topological terms for each node:
______________________________________________ (a) Point symbol: {442.672.839}
Extended point symbol:
[4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.6(2).6(2).6(2).6(2).6(2).6
(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).
6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4)
.6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(4).6(6).6(6).6(6).6(6).6(6).6(6).6(6).6(6).6(6).6(6).6(6
).6(6).8(48).8(48).8(48).8(48).8(48).8(48).8(48).8(48).8(48).8(48).8(48).8(48).8(68).8(68).8(68).8(68).8(
68).8(68).8(16).8(16).8(16).8(16).8(16).8(16).8(20).8(20).8(20).8(20).8(20).8(20).8(32).8(32).8(32).8(4
8).8(48).8(48).8(48).8(48).8(48)]
Coordination sequence: 18 12 132 42 366 92 720 162 1194 252
TD10: 2991
______________________________________________ (b) Point symbol: {43}
Extended point symbol: [4.4(3).4(3)]
Coordination sequence: 3 44 22 214 61 502 120 910 199 1438
TD10: 3514
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Supplementary Figure 31. Expansion of the organic linker (in the present examples by addition of ethynes or benzene rings), along several independent parameters is geometrically compatible with the
gea net, and can result in a series of isoreticular MOFs related to the parent gea topology.
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Structural details
Supplementary Table 1. Crystal data and structure refinement conditions for Tb hexanuclear cluster.
Identification code
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system, space group
Unit cell dimensions
Volume
Z, Calculated density
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Limiting indices
Reflections collected / unique
Completeness to theta = 66.43
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
Tb hexanuclear cluster
C80 H59 F11 N2 O37 Tb6
2802.81
100(2) K
1.54178 Å
Tetragonal, I4/m
a = 15.2613(9) A alpha = 90 deg.
b = 15.2613(9) A beta = 90 deg.
c = 19.9030(15) A gamma = 90 deg.
4635.6(5) Å3
2, 2.008 Mg/m3
22.975 mm-1
2676
0.04 x 0.02 x 0.02 mm
6.05 to 66.43 deg.
-15<=h<=18, -18<=k<=16, -23<=l<=23
15561 / 2088 [R(int) = 0.0459]
98.7 %
Semi-empirical from equivalents
0.6565 and 0.4601
Full-matrix least-squares on F2
2088 / 42 / 129
1.080
R1 = 0.0435, wR2 = 0.1304
R1 = 0.0509, wR2 = 0.1384
0.779 and -0.705 e.A-3
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Supplementary Figure 32. Ortep representation of the asymmetric unit of cuo-cluster (Tb: purple, C: gray, O: red, N: blue, F: green, H: white).
Running the related cif file into checkcif gives the following B alerts:
1) PLAT201_ALERT_2_B: Isotropic non-H Atoms in Main Residue(s) ....... 6
This alert is due to the fact disordered atoms have been refined isotropically.
2) PLAT220_ALERT_2_B: Large Non-Solvent C Ueq(max)/Ueq(min) = 6.0 PLAT220_ALERT_2_B: Large Non-Solvent O Ueq(max)/Ueq(min) = 4.4 PLAT222_ALERT_3_B: Large Non-Solvent H Uiso(max)/Uiso(min) = 8.1
These alerts are related to the presence of disorder in the structure.
3) PLAT420_ALERT_2_B: D-H Without Acceptor O1 - H1
This alert is explained by the fact it was not possible to locate Hydrogen bond acceptor at the relevant position.
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Supplementary Table 2. Crystal data and structure refinement conditions for gea-MOF-1.
Identification code
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system, space group
Unit cell dimensions
Volume
Z, Calculated density
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Limiting indices
Reflections collected / unique
Completeness to theta = 65.06
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
gea-MOF-1
C162 H90 O47 Y9
3588.53
100(2) K
1.54178 Å
Hexagonal, P63/mmc
a = 22.2055(11) Å alpha = 90 deg.
b = 22.2055(11) Å beta = 90 deg.
c = 33.1729(17) Å gamma = 120 deg.
14165.6(12) Å3
2, 0.841 g.cm-3
2.734 mm-1
3578
0.11 x 0.08 x 0.03 mm
3.52 to 65.06 deg.
-25<=h<=22, -20<=k<=21, -35<=l<=33
37133 / 4302 [R(int) = 0.1066]
96.5 %
0.9225 and 0.7530
Full-matrix least-squares on F2
4302 / 46 / 163
0.978
R1 = 0.0735, wR2 = 0.1998
R1 = 0.1102, wR2 = 0.2153
0.849 and -0.722 e. Å-3
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Supplementary Figure 33. Ortep representation of the asymmetric unit in gea-MOF-2 (Y: purple, C: gray, O: red, H: white) Ligand is disordered over two positions.
Running the related cif file into checkcif gives the following B alerts:
1) PLAT201_ALERT_2_B: Isotropic non-H Atoms in Main Residue(s) = 3
This alert is due to the fact disordered atoms have been refined isotropically.
2) PLAT220_ALERT_2_B: Large Non-Solvent O Ueq(max)/Ueq(min ) = 5.2
This alert is caused by the disorder. O atoms of the cluster have very low values of Ueq as compared to the rest of O atoms, leading to large O Ueq(max)/Ueq(min ).
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Supplementary Table 3. Crystal data and structure refinement conditions for gea-MOF-2.
Identification code
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system, space group
Unit cell dimensions
Volume
Z, Calculated density
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Limiting indices
Reflections collected / unique
Completeness to theta = 33.406
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
gea-MOF-2
C72 H35 Cu3 N O15
1344.63
150(2) K
1.54178 Å
Hexagonal, P63/mmc
a = 37.1384(13) Å alpha = 90 deg.
b = 37.1384(13) Å beta = 90 deg.
c = 74.478(2) Å gamma = 120 deg.
88963(8) Å3
12, 0.301 g.cm-3
0.373 mm-1
8172.0
0.06 x 0.03 x 0.02 mm
2.372 to 66.812 deg.
-26<=h<=25, -25<=k<=26, -44<=l<=53
85124 / 6223 [R(int) = 0.1147]
99.9 %
0.747 and 0.558
Full-matrix least-squares on F2
6223 / 471 / 517
1.020
R1 = 0.0638, wR2 = 0.1697
R1 = 0.0969, wR2 = 0.1846
0.29 and -0.21 e.A-3
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Supplementary Figure 34. Ortep representation of the asymmetric unit in gea-MOF-2 (Cu: purple, C: gray, O: red, N: blue, H: white). Ligand is disordered over two positions.
Running the related cif file into checkcif gives the following A and B alerts:
1) THETM01_ALERT_3_A: The value of sin(theta_max)/wavelength is less than 0.550. Calculated sin(theta_max)/wavelength = 0.3571
The crystal of gea-MOF-2 diffracted only up to 1.4Å resolution. The possible reason is the disorder of ligand and solvent present in structural voids.
2) PLAT023_ALERT_3_A: Resolution (too) Low [sin(theta)/Lambda < 0.6] = 33.41 Degree
The crystal of gea-MOF-2 diffracted only up to 1.4Å resolution. The possible reason is the disorder of ligand and solvent present in structural voids.
3) PLAT780_ALERT_1_A: Coordinates do not Form a Properly Connected Set.
Coordinates do form properly connected set. This alert might be due to a Platon issue.
4) PLAT242_ALERT_2_B: Low Ueq as Compared to Neighbors for Cu1.
The oxygen atoms in the axial position of paddle wheel are disordered having larger Ueq values.
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Gas sorption experiments Low pressure sorption data
Supplementary Figure 35. a) Nitrogen sorption isotherm at 77 K and b) evolution of the surface areas and pore volume in gea-MOF-1 depending on the activation temperature.
Supplementary Figure 36. a) Argon sorption isotherm at 87 K and b) pore size distribution from Ar sorption isotherm at 87 K (spher./cylind,NLDFT model, ads.).
Experimental BET surface (1490 m2.g-1) area and pore volume (0.58 cm3.g-1) are in a good agreement
(14%, 17% lower respectively) with the theoretical values (theo SBET=1730 m2.g-1, theo pore
volume=0.71 cm3.g-1). These values are in the range of the experimental error, and DMA+ cations (not
accurately localized) were not considered for the calculation of theoretical values.
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Supplementary Figure 37. a) Hydrogen sorption isotherms collected at 77 K and 87 K and b) the isosteric heat of adsorption (Qst) calculated from the corresponding isotherms using the Clausius-
Clapeyron equation.
Supplementary Figure 38. a) CO2 sorption isotherms and b) Qst of CO2 adsorption calculated from the corresponding isotherms using the Clausius-Clapeyron equation.
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Supplementary Figure 39. a) CO2 sorption isosters for gea-MOF-1 and b) Qst of CO2 calculated from the isosters.
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High pressure sorption data
Supplementary Figure 40. . a) Gravimetric CH4 sorption isotherms at 298 K and b) volumetric CH4 sorption isotherms at 298 K.
Supplementary Figure 41. a) Gravimetric CO2 sorption isotherms at 298 K and b) volumetric CO2 sorption isotherms at 298 K.
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H2 adsorption at 77 K was high pressure up to 50 bars. The corresponding uptake (Supplementary
Figure 22), mainly governed by pore filling is 6.2 wt%. In these conditions, the absolute H2 adsorbed
phase density exceeded slightly (within the experimental errors) the H2 liquid phase density
(0.074 g.cm-3).
Supplementary Figure 42. a) Gravimetric H2 sorption isotherms at 77 K and b) adsorbed phase density H2 sorption isotherms at 77 K.
Supplementary Figure 43. a) CO2, CH4, N2 and H2 sorption isotherms at 298 K and b) IAST calculated selectivity for CO2 over CH4, N2 and H2.
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Supplementary Table 4. Volumetric CH4 working capacity using adsorption and desorption at 5 bar and 35 bar, respectively for gea-MOF-1, USTA-20, NU-125 and HKUST-1.
Adsorbent
Estimated CH4 adsorption
uptake at 5 bar cm3 (STP)/cm3
Estimated CH4 adsorption
uptake at 35 bar cm3 (STP)/cm3
Working storage uptake
cm3 (STP)/cm3
gea-MOF-1 40 140 100 UTSA-20 100 180 80 HKUST-1
NU-125 75 50
225 170
150 120
Supplementary Table 5. Volumetric CH4 working capacity using adsorption and desorption at 5 bar and 50 bar, respectively for gea-MOF-1, USTA-20, NU-125 and HKUST-1.
Adsorbent
Estimated CH4 adsorption
uptake at 5 bar cm3 (STP)/cm3
Estimated CH4 adsorption
uptake at 50 bar cm3 (STP)/cm3
Working storage uptake
cm3 (STP)/cm3
gea-MOF-1 40 162 122 UTSA-20 100 180 80 HKUST-1
NU-125 75 50
250 220
175 170
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Catalysis studies
Experimental procedure for the synthesis of cyclic carbonates 2a-d using catalyst gea-MOF-1
A Mettler Toledo ReactIR 45/MultiMax RB04-50 station mounting 50 mL stainless steel autoclaves was
charged under a protective atmosphere with gea-MOF-1 (60 mg, corresponding to 0.15 mmol of
yttrium) and TBAB (48.3 mg, 0.15 mmol) at 25 °C. Epoxide 1 (100 mmol) was added and the solution
was mechanically stirred at 800 rpm. CO2 was added until the internal pressure in the system reached 18
bar at 25 °C .The temperature of the reactor was then raised to 120 °C, with the internal pressure
reaching 20 bar. After 6 h the reactor was allowed to cool to room temperature, placed in an ice bath,
whereby the pressure was released slowly over time. A sample of the reaction mixture was withdrawn
and analyzed by 1H NMR to determine the conversion.
Catalysis products 2a (CAS: 108-32-7); 2b (CAS: 4437-85-8); 2c (CAS: 4427-92-3); 2d (CAS: 2463-
45-8) are known compounds and the 1H NMR and 13C NMR spectra obtained by us were consistent with
literature. The spectral data for compound 2a are reported as an example:
4-Methyl-1,3-dioxolan-2-one, (2a): 1H NMR (400 MHz, CDCl3, 20 °C): δ = 4.82 (m, 1H, OCH), 4.55
(t, 1H, J = 8.3 Hz, OCH2), 4.00 (dd, 1H, J = 7.8, 7.9 Hz, OCH2), 1.47 (d, 3H, J = 6.3 Hz, CH3) ppm. 13C
NMR (100 MHz, CDCl3, 20 °C): δ = 155.4 (C=O), 74.6 (CHO), 70.6 (OCH2), 19.1 (CH3) ppm.
Determination of the conversion
Supplementary Scheme 3. Synthesis of cyclic carbonates from CO2 and epoxides catalyzed by gea-MOF-1
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For each reaction, conversion was determined by comparison of the 1H-NMR integrals of the
corresponding OCH protons in the starting material (1Ha) and in the product (1Hb) according to equation
8 and Supplementary Table 6.
(8)
Supplementary Table 6. Chemical shifts (δ, ppm) for the OCH protons in the epoxides and in the corresponding carbonates (in CDCl3).
Epoxide δOCH (CDCl3)(epoxide, 1Ha) δOCH (CDCl3)(carbonate, 1Hb)
2a 2.92 4.82
2b 2.92 4.70
2c 3.80 4.67
2d 3.22 4.97
Catalyst Recovery
The catalyst, i.e. gea-MOF-1, was separated from the mixture at the end of the reaction via vacuum
filtration. The solid was washed abundantly with dichloromethane (DCM) and MeOH, placed in a vial
and soaked in MeOH for at least 6 h and subsequently dried under vacuum at room temperature. The
quantity of catalyst recovered after each cycle corresponds to ca. 95% of the initial amount, and was still
crystalline, as confirmed by PXRD (Supplementary Figure 44).
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Supplementary Figure 44. Experimental and calculated PXRD patterns for gea-MOF-1 after catalysis cycles, indicating the crystallinity is retained.
Study on yttrium leaching and supernatant activity
In order to exclude the contribution of homogeneous Y-species to the catalytic performance of gea-
MOF-1, the amount of Y present in the carbonate product obtained after the experiment described below
was determined by mean of ICP-MS.
gea-MOF-1 (25 mg; corresponding to 0.0625 mmol of Y) and TBAB (40.3 mg, 0.125 mmol) were
employed to promote the cycloaddition reaction of propylene oxide (7 mL, 100 mmol) using the
experimental procedure reported above. At the end of the reaction (6h) the content of the reaction vessel
was filtrated to remove the catalyst and the liquid phase was evaporated under reduced pressure to afford
3.6 g (yield = 35 %) of propylene carbonate (δPC = 1.2 g.mL-1; VPC = 3 mL). An aliquot of the product
was analyzed by ICP-MS (Elan DRC-II, PE SCIEX mounting a SeaSpray-nebulizer and a cyclonic
spray chamber; the sample and the standard solutions were diluted in pure nitric acid and water) which
determined a concentration of 25 ppm (μg/mL) of Y in the propylene carbonate sample after the
reaction. This corresponds to a total of 75 μg (0.84 μmol) of Y present in solution after reaction (1.3 %
of the initial amount of Y). The coordination sphere of this small amount of potentially leached Y is not
known, and it cannot be excluded that it correspond to small crystals of gea-MOF-1 that could not be
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separated from the viscous propylene carbonate product and were digested by nitric acid during the ICP-
MS analysis. Soluble gea-MOF-1 precursor, Y(NO3)3 (0.84 μmol) in the presence of TBAB (40.3 mg,
0.125 mmol) failed to provide propylene carbonate under the same reaction conditions applied for gea-
MOF-1. In a further experiment, a portion (1.2 g) of the propylene carbonate supernatant produced (3.6
g) from the cycloaddition of CO2 and propylene oxide (7 mL) catalyzed by gea-MOF-1 (18.0 mg) and
TBAB (29 mg, 0.09 mmol) under the reaction condition reported above was added to PO (7 mL) and the
mixture stirred for 6 h at 120 °C under 20 bar CO2. After catalyst filtration, the residual propylene oxide
was removed by rotary evaporation. The initial quantity of propylene carbonate (1.2 g) was recovered
unchanged, showing that no catalytic activity could be found in the supernatant solution. This result,
along with the very limited amount of Y leached and the fact the structure of gea-MOF-1 is retained
after catalysis (Supplementary Figure 44), in addition to the excellent reusability of the recovered
catalyst, confirms that the catalytic activity reported resides in the heterogeneous gea-MOF-1.
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