SUPPLEMENTARY INFORMATION10.1038... · NATURE CHEMISTRY | . 1. SUPPLEMENTARY INFORMATION. DOI:...

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NATURE CHEMISTRY | www.nature.com/naturechemistry 1 SUPPLEMENTARY INFORMATION DOI: 10.1038/NCHEM.1982 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 Eddaoudi 1 * 1 Functional Materials Design, Discovery and Development Research Group (FMD 3 ), 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. 2 Kaust Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955- 6900, Kingdom of Saudi Arabia. 3 Department of Chemistry, University of South Florida, 4202 East Fowler Ave., Tampa, Florida, 33620, United States of America. *e-mail: [email protected] © 2014 Macmillan Publishers Limited. All rights reserved.

Transcript of SUPPLEMENTARY INFORMATION10.1038... · NATURE CHEMISTRY | . 1. SUPPLEMENTARY INFORMATION. DOI:...

Page 1: SUPPLEMENTARY INFORMATION10.1038... · NATURE CHEMISTRY |  . 1. SUPPLEMENTARY INFORMATION. DOI: 10.1038/NCHEM.1982. S1 Discovery and introduction of a (3,18)-connected net

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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

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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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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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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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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 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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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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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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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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Supplementary Scheme 2. Synthesis of the hexacarboxylate ligand L8 (H6L).

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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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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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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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