Synthesis and structural comparisons of five new fluorinated metal organic frameworks (F-MOFs

PAPER www.rsc.org/crystengcomm | CrystEngComm

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Synthesis and structural comparisons of five new fluorinated metal organicframeworks (F-MOFs)†

Pradip Pachfule, Chandan Dey, Tamas Panda and Rahul Banerjee*

Received 25th August 2009, Accepted 8th December 2009

First published as an Advance Article on the web 14th January 2010

DOI: 10.1039/b917483d

A series of fluorinated metal–organic frameworks (F-MOFs) have been successfully synthesized under

hydrothermal condition using 4,40-(hexafluoroisopropylidene) bis(benzoic acid) (C17H10F6O4,

H2hfbba) as a flexible dicarboxylate building block, Cu+2 and various heterocyclic co-ligands. These

F-MOFs formulated as [Cu(hfbba)(phen)2]$2(H2hfbba)(H2O)(HCO2) (F-MOF-1), [Cu(hfbba)2(2,20-

bipy)2(H2O)] (F-MOF-2), [Cu(hfbba)(4,40dime-2,20-bipy)(HCO2)]$(hfbba)(H2O) (F-MOF-3),

[Cu2(hfbba)2(3-mepy)2]$(DMF)2(3-mepy) (F-MOF-4), and [Cu(hfbba)2(phen)2]$0.5(DMF) (F-MOF-

5) (hfbba ¼ 4,40-(Hexafluoroisopropylidene) bis(benzoate), phen ¼ 1,10-phenanthroline; 2,20-bipy ¼2,20-bipyridine; 4,40dime-2,20-bipy ¼ 4,40dimethyl 2,20-bipyridine; 3-mepy ¼ 3-methyl-pyridine and

DMF ¼ dimethyl formamide) display interesting H-bonded, 1D and 2D structural features. All these

F-MOFs were structurally determined by single-crystal X-ray diffraction. F-MOF-1 and 5 form

a distorted octahedral Cu+2 secondary building unit (SBU). F-MOF-5 forms a one-dimensional

architecture constructed from Cu2+ ions bridged by phen anions and two types of 4 hfbba ligands while

in F-MOF-1, two among the three acid co-ligands are not coordinated with Cu2+ ions. F-MOF-2

displays dinuclear SBUs within the three-dimensional frameworks whereas F-MOF-3 displays

mononuclear SBUs and forms a one-dimensional chain. F-MOF-4 display a interesting 2D framework

with conventional Cu2(CO2)4 paddle wheel SBU. In the crystal structures four hfbba ligands, each

coordinated to a dicopper paddlewheel unit via one of their carboxylate groups. Solid-state properties

such as UV-vis and thermal stability of F-MOF-1–5 have also been studied.

Introduction

Metal–organic frameworks (MOFs) have received considerable

interest in the last two decades.1 The combination of multi-

functional organic linkers with multinuclear metal complexes

acting as nodes has emerged as a modular concept for systematic

design of porous solids with specific applications in separation,

storage, heterogeneous catalysis.2 The work by Yaghi, Long,

Cheetham, Kitagawa, Ferey and others have succeeded in

highlighting the model of carboxylate-based systems in the

generation of highly stable, porous, functionalized crystalline

materials that has surface areas and micropore volumes much

higher than the traditional molecular sieves such as zeolites and

activated carbons.3 Although a great variety of MOFs with

diverse compositions and structures have been reported,

however, to date, the control of product architecture remains

a major challenge in this field due to the fact that the self-

assembly process is frequently influenced by the type of the

ligand, metal-to-ligand ratio, chemical and geometrical

Physical Materials Chemistry Division, National Chemical Laboratory, DrHomi Bhaba Road Pune, 411008, India. E-mail: [email protected];Fax: + 91-20-25902636; Tel: + 91-20-25902535

† Electronic supplementary information (ESI) available: Synthesisprocedures, single-crystal X-ray data collection, structure solution andrefinement procedures, thermal stability and UV of F-MOFs. CCDCreference numbers 745103–745107. For ESI and crystallographic datain CIF or other electronic format see DOI: 10.1039/b917483d

1600 | CrystEngComm, 2010, 12, 1600–1609

preferences of the metal ion, solvent and temperature of synthesis

and other factors.4

Recently researchers have shown interest into the possibility of

synthesizing fluorinated metal–organic frameworks (F-MOFs)

using perfluorinated polycarboxylate ligands.5 These F-MOFs

could emerge as a better H2-storage material as they bind

hydrogen more strongly and efficiently than their non-fluori-

nated counterparts.6 There are only a few reports of MOFs

containing fluorinated carboxylates as perfluorinated carboxyl-

ates7 are significantly more acidic than non-fluorinated carboxy-

lates, and subsequently less soluble in common organic solvents.

Fluorinated acids are also less stable than their non-fluorinated

analogues and it has been found that they often decompose at

temperatures commonly used to form MOFs of higher dimen-

sionality (125–180 �C).

In this contribution, we will describe our recent research on the

synthesis, crystal structures, and properties of a series of

F-MOFs with 4,40-(hexafluoroisopropylidene) bis(benzoic acid)

(C17H10F6O4, H2hfbba) as a flexible dicarboxylate building

block, Cu+2 and various heterocyclic co-ligands (Scheme 1).

These F-MOFs formulated as [Cu(hfbba)(phen)2]$2(H2hfbba)-

(H2O)(HCO2) (F-MOF-1), [Cu(hfbba)2(2,20-bipy)2(H2O)]

(F-MOF-2), [Cu(hfbba)(4,40dime-2,20-bipy)(HCO2)]$(hfb-

ba)(H2O) (F-MOF-3), [Cu2(hfbba)2(3-mepy)2]$(DMF)2(3-mepy)

(F-MOF-4), and [Cu(hfbba)2(phen)2]$0.5(DMF) (F-MOF-5)

(hfbba ¼ 4,40-(Hexafluoroisopropylidene) bis(benzoate), phen ¼1,10-phenanthroline; 2,20-bipy ¼ 2,20-bipyridine; 4,40dime-2,20-

bipy ¼ 4,40dimethyl 2,20-bipyridine; 3-mepy ¼ 3-methyl-pyridine

This journal is ª The Royal Society of Chemistry 2010

http://dx.doi.org/10.1039/b917483d

Scheme 1 Schematic diagram showing solvent dependence on the

synthesis of F-MOFs.

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and DMF¼ dimethylformamide) display interesting 1D, 2D and

3D structural features. The inclusion of such second links assists

in forming structures containing the fluorinated ligand and also

helps reduce the rather significant increase in density. Thermal

stability, PXRD and UV-vis spectra of these F-MOFs have also

been investigated.

Experimental

Materials and general methods

All reagents and solvents for synthesis and analysis were

commercially available and used as received. The Fourier

transform (FT) IR spectra (KBr pellet) were taken on an PER-

KIN ELMER FT-IR SPECTRUM (Nicolet) spectrometer.

Powder X-ray diffraction (PXRD) patterns were recorded on

a Phillips PNAlytical diffractometer for Cu Ka radiation

(l ¼ 1.5406 �A), with a scan speed of 2� min�1 and a step size of

0.02� in 2q. Thermogravimetric experiments (TGA) were carried

out in the temperature range of 25–700 �C on a SDT Q600

TG-DTA analyzer under N2 atmosphere at a heating rate of

10 �C min�1. Solid-state UV spectra were measured at room

temperature on a PERKIN ELMER Precisely Lambda 650

spectrometer.

Synthesis of F-MOF-1 to 5

[Cu(hfbba)(phen)2]$2(H2hfbba)(H2O)(HCO2) (F-MOF-1).

Hydrothermal reaction of Cu(NO3)2$3H2O (0.029 g, 0.12 mmol)

with 1,10-phenanthroline (0.024 g, 0.12 mmol) and excess

H2hfbba (0.196 g, 0.50 mmol) in a 23 mL acid-digestion bomb

using de-ionized water (7 mL) at 120 �C for 3 d produced blue

coloured crystals of F-MOF-1 in 40% yield (0.0116 mg based on

Cu). Crystals were collected by filtration and dried in air

(10 min).

FT-IR (KBr 4000–400 cm�1): 3655 (s), 3093 (w), 1942 (w), 1701

(s), 1598 (s), 1554 (s), 1395 (s), 1326 (w), 1250 (m), 1211 (w), 1177

(w), 1019 (w), 1291 (w), 929 (w), 843 (m), 778 (m), 744 (m),

723 (m).


[Cu(hfbba)2(2,20-bipy)2(H2O)] (F-MOF-2). 0.5 mL 2,20-bipyr-

idyl stock solution (0.20 M) and 1.5 mL H2hfbba stock solution

(0.20 M) were mixed in a 5 mL vial. To this solution was added

0.5 mL Cu(NO3)2$3H2O stock solution (0.20 M). The vial was

capped and heated to 85 �C for 96 h. The mother liquor was

decanted and the products were washed with DMF (15 mL) three

times. Blue coloured crystals of F-MOF-2 were collected by

filtration and dried in air (10 min) (yield: 30%; 0.0072 mg based

on Cu).

FT-IR (KBr 4000–400 cm�1): 3040 (s), 2554 (w), 1945 (w), 1817

(w), 1689 (s), 1626 (s), 1557 (m), 1515 (w), 1482 (w), 1390 (m),

1289 (w), 1213 (w), 1175 (m), 1140 (s), 1068 (w), 1020 (m), 946

(w), 846 (w), 779 (m), 749 (m), 727 (s), 589 (w), 541 (w), 496 (w).

[Cu(hfbba)(4,4 0dime-2,2 0-bipy)(HCO2)]$(hfbba)(H2O)

(F-MOF-3). Hydrothermal reaction of Cu(NO3)2$3H2O

(0.029 g, 0.12 mmol) with 4,40-dimethyl-2,20- bipyridine (0.022 g,

0.12 mmol) and excess H2hfbba (0.196 g, 0.50 mmol) in a 25 mL

acid-digestion bomb using de-ionized water (7 mL) at 120 �C for

3 d produced blue coloured crystals of F-MOF-3 in 60% yield

(0.0174 mg based on Cu). Crystals were collected by filtration

and dried in air (10 min).

FT-IR (KBr 4000–400 cm�1): 3695 (br), 3557 (m), 3090 (w),

2496 (w), 2094 (w), 1942 (w), 1824 (w), 1698 (m), 1681 (m), 1591

(w), 1543 (m), 1399 (s), 11326 (w), 1290 (s), 1257 (w), 1172 (w),

1021 (w), 960 (w), 860 (w), 779 (m), 745 (w), 723 (m), 519 (w).

[Cu2(hfbba)2(3-mepy)2]$(DMF)2(3-mepy) (F-MOF-4). 0.5 mL

3-methyl-pyridine stock solution (0.20 M) and 1.5 mL H2hfbba

stock solution (0.20 M) were mixed in a 5 mL vial. To this

solution was added 0.5 mL Cu(NO3)2$3H2O stock solution (0.20

M). The vial was capped and heated to 85 �C for 96 h. The

mother liquor was decanted and the products were washed with

DMF (15 mL) three times. Blue coloured crystals of F-MOF-4

were collected by filtration and dried in air (10 min) (yield: 50%;

0.0120 mg based on Cu).

FT-IR (KBr 4000–400 cm�1): 3676 (br), 3068 (w), 3935 (m),

2657 (w), 2548 (w), 2331 (s), 1944 (m), 1816 (w), 1683 (m), 1632

(w), 1561 (w), 1410 (s), 1291 (w), 1239 (s), 1174 (w), 1090 (w),

1020 (w), 971 (w), 929 (w), 846 (m), 780 (s), 748 (w), 706 (w),

514 (m), 494 (w).

[Cu(hfbba)2(phen)2]$0.5(DMF) (F-MOF-5). 0.5 mL 1,10-phe-

nanthroline stock solution (0.20 M) and 1.5 mL H2hfbba stock

solution (0.20 M) were mixed in a 5 mL vial. To this solution was

added 0.5 mL Cu(NO3)2$3H2O stock solution (0.20 M). The vial

was capped and heated to 85 �C for 96 h. The mother liquor was

decanted and the products were washed with DMF (15 mL) three

times. Blue coloured crystals of F-MOF-4 were collected by filtra-

tion and dried in air (10 min) (yield: 68%; 0.0163 mg based on Cu).

FT-IR (KBr 4000–400 cm�1): 3680 (br), 3056 (s), 2937 (m),

2510 (w), 1941 (m), 1813 (w), 1683 (s), 1599 (m), 1557 (w), 1519

(w), 1411 (s), 1253 (w), 1211 (w), 1172 (w), 1138 (w), 1019 (m), 971

(w), 845 (s), 778 (s), 748 (w), 725 (m), 557 (w), 515 (w), 495 (w).

X-Ray crystallography

All single crystal data were collected on a Bruker SMART APEX

three circle diffractometer equipped with a CCD area detector

CrystEngComm, 2010, 12, 1600–1609 | 1601


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(Bruker Systems Inc., 1999)8 and operated at 1500 W power

(50 kV, 30 mA) to generate Mo Ka radiation (l ¼ 0.71073 �A).

The incident X-ray beam was focused and monochromated using

Bruker Excalibur Gobel mirror optics. Crystals of the F-MOFs

reported in the paper were mounted on nylon CryoLoops

(Hampton Research) with Paraton-N (Hampton Research).

Crystals were flash frozen to 100(2) K in a liquid nitrogen cooled

stream of nitrogen. Data were integrated using Bruker SAINT

software.9 Data were subsequently corrected for absorption by

the program SADABS.10 The space group determinations and

tests for merohedral twinning were carried out using XPREP.11

In all cases, the highest possible space group was chosen. All

structures were solved by direct methods and refined using the

SHELXTL-97 software suite.12 Atoms were located from itera-

tive examination of difference F-maps following least squares

refinements of the earlier models. Hydrogen atoms were placed in

calculated positions and included as riding atoms with isotropic

displacement parameters 1.2–1.5 times Ueq of the attached C

atoms. Data were collected at 298(2) K for F-MOF-5. For the

other four F-MOFs presented in this paper data collection took

place at 100(2) K. This lower temperature was considered to be

optimal for obtaining the best data. All structures were examined

using the Adsym subroutine of PLATON13 to assure that no

additional symmetry could be applied to the models. All ellip-

soids in ORTEP diagrams are displayed at the 50% probability

level unless noted otherwise. The ESI contains a detailed data

collection strategy and crystallographic data for the five F-MOFs

reported in this paper.† Crystal data and details of data collec-

tion, structure solution and refinement are summarized in

Table 1.

Results and discussion

Synthesis and characterization

Direct solution reactions at room temperature give rise to

a microcrystalline precipitate in most MOF syntheses.14 The

hydrothermal method has been demonstrated to be a very

promising technique for growing MOF crystals. Thus, hydro-

thermal methods were applied to obtain larger single crystals

suitable for X-ray diffraction. H2hfbba is sparingly soluble in

water at room temperature. To obtain pure crystals of F-MOF-1

and 3, a strong stirring of the mixture in de- ionized water is

necessary before it is transferred to an acid-digestion bomb for

hydrothermal reaction. In this work, two synthetic pathways

were applied to prepare these F-MOFs. Complexes F-MOF-1

and 3 were obtained by hydrothermal reaction of the ligand with

Cu(NO3)2$3H2O in water in a acid digestion bomb at higher

temperature (120 �C), whereas F-MOF-2, 4 and 5 were synthe-

sized by hydrothermal reaction in a glass vial at lower temper-

ature (85 �C). In each synthetic case, an approximate Cu/

H2hfbba/heterocyclic co-ligands composition of 1/5/1 was found

to produce best yield of the product. All these complexes are

insoluble in common organic solvents. The compositions of

F-MOF-1 to 5 were determined by IR, and single-crystal X-ray

diffraction techniques. The phase purities of the bulk samples

were further identified by powder X-ray diffraction (PXRD)

patterns, which display essential similarity to those of the

calculated ones (see Fig. 7).

1602 | CrystEngComm, 2010, 12, 1600–1609

For the IR spectra, the broad bands centered at ca. 3550 cm�1

indicate the O–H stretching of water for F-MOF-1 and 3.

Notably, in the IR spectra of complexes F-MOF-1 and 3, the

presence of characteristic absorption bands of carboxyl, which

appears at 1700 cm�1 for the free ligand, reveals its presence in

the crystal lattice, whereas the absence of the same absorption

bands for F-MOF-4 and 5 reveals its complete deprotonation.

The strong absorption peak at 1679 cm�1 (a significant shift in

comparison with that of the free ligand) should be ascribed to

metal coordination of the carboxyl group. The coexistence of

both carboxyl and carboxylate groups in F-MOF-1 and 3 can

also be validated by the crystal structure.

Structural description

Crystal structure of [Cu(Hhfbba)(phen)2]$2(H2hfbba)-

(H2O)(HCO2) (F-MOF-1). The asymmetric unit of F-MOF-1

(space group P21/n) consists of one crystallographically inde-

pendent Cu+2 ion, one Hhfbba (i.e. singly protonated H2hfbba),

two free H2hfbba, two phen, one formic acid and one lattice

water molecule. Each Cu+2 ion is surrounded by four nitrogen

atoms from two chelating phen ligands and two oxygen atoms

from one Hhfbba anion, composing a slightly distorted octahe-

dral geometry with Cu–O distances ranging from 1.984(2) to

2.641(2) �A and Cu–N distances ranging from 2.014(3) to 2.272(3)�A (Fig. 2a). One carboxylate of the H2hfbba adopts a bidentate

chelating mode and the other remains un-coordinated. The one-

dimensional structure of F-MOF-1 consists of layers of Cu+2 ions

coordinated to the H2hfbba ligands and phen molecules. Two of

this octahedral Cu(phen)2(Hhfbba) units are attached by

hydrogen bonds between the terminal Hhfbba and uncoordi-

nated H2hfbba groups to form a 1D hydrogen-bonding frame-

work (Fig. 2c and 2d). In complex F-MOF-1, the free carboxylic

acids (four of them) are H-bonded in a catemeric fashion to form

a (COOH)4 cluster (Fig. 2b).15 Hydrogen bonds involving the

lattice water molecules as donors join both kinds of carboxylic

acids to generate a two-dimensional organization in the ab plane.

The average O–H/O distance in this finite hydrogen bonded

network is 1.700(2) �A and the average angle is 172.2 �A (see ESI,

Table S2).† The residual positive charge on the metal ion remains

as it binds to only one formate anion (HCO2�).

Crystal structure of [Cu(hfbba)2(2,20-bipy)2(H2O)] (F-MOF-2).

As shown in Fig. 3a, the asymmetric unit of F-MOF-2 (space

group P21/n) comprises one crystallographically independent

Cu+2 ion, one hfbba ligand, one 2,20-bipy ligand, and a lattice

water molecule. Each Cu+2 ion octahedrally surrounded by two

nitrogen atoms from the bridging 2,20-bipy ligands, three oxygen

atoms from three hfbba ligands and one oxygen atom from the

coordinated water molecule. Two copper atoms are octahedrally

coordinated by eight oxygen atoms, six of them from hfbba

anions, and two trans water molecules and four nitrogen from

two bridging 2,20-bipy ligands creating a dicopper SBU (Fig. 3a).

The Cu–O and Cu–N bonds are in the range of 1.945(2)–2.797(4)

and 2.003(4)–2.005(2) �A, respectively. The H2hfbba ligands

bridge metal centers in two directions, forming a grid-like two

dimensional sheet (Fig. 3b). In complex F-MOF-2, CF3 groups

interacts with each other to form a type II F2C–F/FCF2 syn-

thon (d, 3.251(2) �A; d, 2.748(3) �A; q1, 160.1�, q2, 99.5�) (Fig. 3c).16



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This journal is ª The Royal Society of Chemistry 2010 CrystEngComm, 2010, 12, 1600–1609 | 1603

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Fig. 1 Different SBU’s discussed in this paper.

Fig. 2 Crystal structure of F-MOF-1. (a) Polyhedral representation of

the SBU showing the coordination environment of Cu(II) Cu (brown), N

(blue), O (red), C (black), F (green). (b) H-bonded (COOH)4 cluster in

F-MOF-1. (c) Hydrogen bonding between hfbba and octahedral

Cu(phen)2(Hhfbba) units. (d) Hydrogen-bond motifs of H2hfbba

between the coordination layers. (e) Packing diagram of F-MOF-1 in

space fill model (view down b axis).


the SBU showing the coordination environment of Cu(II). (b) The hfbba

and 2,20-bipy ligands bridge metal centers in two directions, forming

a layered 2D sheet; (c) packing diagram of F-MOF-3 (view down b axis).

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Crystal structure of [Cu(hfbba)(4,40dime-2,20-bipy)(H-

CO2)]$(hfbba)(H2O) (F-MOF-3). The two-dimensional structure

(space group Pccn) in F-MOF-3 consists of one crystallograph-

ically independent Cu+2 ion atom, two hfbba ligands, one

1604 | CrystEngComm, 2010, 12, 1600–1609

4,40dime-2,20-bipy and one lattice water molecule. Each Cu+2 ion

is surrounded by two nitrogen atoms from the bridging 4,40dime-

2,20-bipy ligand, three oxygen atoms from one and half (one full

hfbba ligand and half hfbba ligand is present in the asymmetric

unit) composing a square pyramidal geometry with Cu–O

distances ranging from 1.934(2) to 2.320(2) �A and Cu–N

distances ranging from 2.001(3) to 2.014(3) �A (Fig. 4a). The

hfbba and 4,40dime-2,20-bipy ligands bridge metal centers in two

directions, forming a grid-like one dimensional sheet (Fig. 4b).

Free H2hfbba molecules pack in the void space between these

grid layers. This alternating MOF–organic–MOF layer

arrangement is unprecedented among this series of F-MOFs. The

one-dimensional parallel interpenetrating network (Fig. 4c) is

reinforced by the existence of other non-covalent interactions

like C–H/F hydrogen bonds (d, 3.408(2) �A; d, 2.536(3) �A; q,

152.9�) (Fig. 4d Table 2).17

Crystal structure of [Cu2(hfbba)2(3-mepy)2]$(DMF)2(3-mepy)

(F-MOF-4). Asymmetric unit of F-MOF-4 (space group P21/c)

comprises two crystallographically independent Cu+2 ion, two




the SBU showing the coordination environment of Cu(II). (b) The hfbba

and 4,40dime-2,20-bipy ligands bridge metal centers in two directions,

forming a grid-like 1D sheet. (c) Interpenetration of two grid like 1D

sheet. (d) Packing diagram of F-MOF-3 (view down b axis).

Fig. 5 Crystal structure of F-MOF-4. (a) Ball and Stick representation

of the SBU showing the paddle-wheel motif of Cu(II); Cu (brown), N

(blue), O (red), C (black), F (green). Two 3-methyl-pyridine ligand

occupy the axial positions. (b) 2D (4,4) coordination layer in F-MOF-4

with Cu(II) paddle-wheel binuclear nodes (view down b axis). Hydrogen

atoms, guest molecules and 3-methyl-pyridines are omitted for clarity. (c)

Coordination layer in F-MOF-4 (view down a axis) showing the 5.5 �A

channels, 3-methyl-pyridine guest molecules occupy the voids inside the

channels.

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hfbba and two 3-mepy ligand, one lattice 3-mepy and three

lattice DMF molecules (Fig. 5a). Both Cu+2 centres have almost

the same coordination environments with a nearly ideal square-

pyramidal sphere (s z 0)18 enclosed by two hfbba ligands and

one 3-methyl-pyridine ligand. The dicopper paddlewheel SBU2c

for F-MOF-4 with the Cu/Cu distance of 2.603(1) �A is shown in

Fig. 5a, expanded to show the four hfbba ligands, each coordi-

nated to a dicopper paddlewheel unit via one of their carboxylate

groups. The second carboxylate group of each H2hfbba ligand

coordinates to another paddlewheel unit, generating the

extended corrugated two dimensional sheet, as shown in Fig. 5b,

two 3-methyl-pyridine ligand occupy the axial positions of the

dicopper paddle wheel SBU. In F-MOF-4, the sheets stack along

the y axis affording square -shaped channels from the sheet

cavities that run through the gross structure (Fig. 5c) similarly

sheets stack along the z axis affording hexagonal channels that

run through the gross structure. The distance between equivalent

atoms in neighbouring sheets is approximately 3.5 �A. The –CF3

groups of H2hfbba ligands are directed to the outside of the

larger square channels whereas DMF and 3-methyl-pyridine

guests reside inside the square shaped and hexagonal channels,

respectively. The pore diameter is approximately 5.5 �A across,

based on the largest sphere that could fit into the pore and be in


contact with the van der Waals surface. Such a large void space

within a framework often leads to molecular entanglement and

two-fold interpenetration. Interestingly we have isolated

a interpenetrated form of F-MOF-4 [Cu2(hfbba)2(3-mepy)2]

(H2O)2(3-mepy) which will be discussed elsewhere.

Crystal structure of [Cu(hfbba)2(phen)2]$0.5(DMF) (F-MOF-

5). The one-dimensional structure of F-MOF-5 (space group

Pbcn) consists of layers of copper ions coordinated to H2hfbba

ligands, phen molecules and disordered DMF ligand. As shown

in Fig. 6a, the asymmetric unit of F-MOF-5 comprises one

crystallographically independent Cu+2 ion, one hfbba ligand, one

phen, and a lattice DMF molecule. Molecular constituents of

F-MOF-5 and 1 are same as they both comprises hfbba ligand

and phen molecule. However, unlike F-MOF-1, each Cu+2 ion is

surrounded by four oxygen atoms from two hfbba anions and

two nitrogen atoms from one chelating phen ligand, composing

a slightly distorted octahedral geometry with Cu–O distances

ranging from 1.953(4) to 2.707(5) �A and Cu–N distances ranging

from 2.002(3) to 2.010(3) �A (Fig. 6a). The structure of F-MOF-5

generate a 1D wavelike chain, extending along the

CrystEngComm, 2010, 12, 1600–1609 | 1605



the SBU showing the coordination environment of Cu(II); (b) corrugated

1D coordination layer in F-MOF-5 towards the ab plane.

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crystallographic a directions incorporating Cu+2 ions coordi-

nated by the hfbba ligand and phen molecules. These chains are

reinforced by the C–F/p interaction [4.091(2) �A; 3.036(3) �A;

134.3�] along the c direction leading to the formation of a 2D

layered structure (Fig. 6b).

The structural analysis of these five copper(II) coordination

polymers derived from the 4,40-(hexafluoroisopropylidene)

bis(benzoic acid) (C17H10F6O4, H2hfbba) as a flexible dicarboxy-

late building block, Cu+2 and various heterocyclic co-ligands led

to several interesting structural features. We primarily used 4,40-

(hexafluoroisopropylidene) bis(benzoic acid) because (a) the

twisted conformation of this link may help forming a possible

helical structure, (b) this flexible dicarboxylate building block

tends to vary the structural feature from one-dimensional to two-

dimensional depending on the type of the heterocyclic co-ligands

attached to the metal,7 (c) the different deprotonated degrees of

the ligands under different reaction conditions may result in

variable coordination modes in the products, (d) long molecular

structure of this primary building unit may lead to the formation

of microporous coordination frameworks with channels. The

influence of the solvent (H2O–DMF) on the formation of the

F-MOFs was also reflected in the structures of the materials.

Fig. 1 describes different SBU’s that has been described in this

paper. F-MOF-2 [Cu(hfbba)2(2,20-bipy)2(H2O)] is a 2D structure

where Cu+2 ion, is coordinated with one hfbba, one 2,20-bipy, and

a lattice water molecule. However, the introduction of the two

–CH3 functionality in 4,40dime-2,20-bipy ligand over 2,20-bipy

leads to the formation F-MOF-3, which is a one dimensional grid

structure reinforced by the C–F/F–C interactions.16 The steric

effect of –CH3 functionality of 4,40dime-2,20-bipy probably

hinders the formation of the octahedral SBU and leads to

a square pyramidal SBU. Overall, when the bulky terminal

1606 | CrystEngComm, 2010, 12, 1600–1609

ligands like phen and 4,40dime-2,20-bipy are introduced

H-bonded or 1D structures are obtained. On the other hand,

when the terminal ligands 2,20-bipy and 3-mepy are introduced

into the systems, the resulting F-MOFs show 2D network struc-

tures. A possible reason for F-MOF-1 being H-bonded compared

to the other F-MOFs reported in this paper could be attributed to

the solvent of synthesis. High polarity of water (3 ¼ 80.0 as

compared to DMF’s 3¼ 38.5) acts to stabilize the separated ionic

species of F-MOF-1 and as a result it forms a H-bonded structure.

Thermal stability and PXRD

To examine the architectural and thermal stability of F-MOFs

reported in this paper, we prepared them at the gram scale to

allow detailed investigation of the aforementioned properties.

Thermal gravimetric analysis (TGA) performed on as-synthe-

sized F-MOF-1 to 5 revealed these compounds high thermal

stability (see ESI, Section S3 for all data and interpretations

regarding guest mobility and thermal stability of F-MOF-1 to

5).† The TGA of compound F-MOF-1, 2, 3 and 5 demonstrates

that the compound has an excellent thermal stability as no

strictly clean weight loss step occurred below 300 �C. This indi-

cates that the co-ordinated water molecules leave the framework

at the point of decomposition. A sharp weight loss at 300 �C

indicates decomposition of the host framework. TGA trace for

F-MOF-4 is totally different from the other F-MOFs reported in

this paper as it possess 2D pores (5.5 �A in diameter). The TGA

trace for F-MOF-1 showed a gradual weight-loss step of 20.3%

(25–200 �C), corresponding to escape of all N,N dime-

thylformamide (DMF) and 3-methylpyridine solvent molecules

trapped in the pores (2 DMF; calcd 18.3%) followed by a plateau

(200–300 �C).

In order to confirm the phase purity of the bulk materials,

powder X-ray diffraction (PXRD) experiments were carried out

on all complexes. The PXRD experimental and computer-

simulated patterns of all of them are shown in the ESI (Fig. S1 to

S5).† As shown in Fig. 7, all major peaks of experimental powder

X-ray patterns (PXRD) of compounds F-MOF-2 to 5 matches

well that of simulated PXRD, indicating their reasonable crys-

talline phase purity. The experimental patterns of F-MOFs

1 have a few unindexed diffraction lines and some slightly

broadened in comparison with those simulated patterns. This is

probably due to the loss of H-bonded water molecule from the

lattice produces a different phase than that obtained in the single

crystalline form. Incidentally, F-MOF-1 showed no weight loss

step occurred below 300 �C also indicates that the loss of

H-bonded water before the TGA experiment. The experimental

patterns of F-MOF-2, -3 -4 and -5 show reduced intensity at

higher 2q (> 20�). This could be due to loss of solvent from the

lattice produces during sample preparation and followed by

slight loss of crystallinity at higher 2q. The occurrence of a few

extra peaks for F-MOF-2, -3 -4 and -5 could be attributed as

a different phase (less than 5% of the bulk) than that obtained in

the single crystalline form.

Adsorption properties of F-MOF-4

The sample of F-MOF-4 was prepared by a thorough washing of

crystals with CHCl3 followed by a evacuation at 120 �C for 3 h.



Fig. 7 Comparison of PXRD patterns of the as-synthesized F-MOFs reported in this paper (red) with the simulated pattern from the single-crystal

structure (black). Overlay of TGA traces of as-synthesized F-MOFs reported in the paper.

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The BET surface area of F-MOF-4 was found to be 196 m2 g�1,

which is quite low and may therefore indicate a slight constric-

tion of the channels after solvent removal. Nitrogen and

hydrogen adsorption isotherms for F-MOF-4 are shown in

Fig. 8. While the volume of hydrogen adsorbed by F-MOF-4 is

rather modest (0.6 wt% H2), but this report once again proves

that hybrid materials containing a per-fluorinated ligand can

emerge as a hydrogen storage materials.

UV-vis properties of F-MOF-1–5

Solid-state luminescent emission spectra of F-MOFs-1 to -5 as

well as the free ligand H2hfbba were recorded at room temper-

ature (Fig. 9). UV-vis absorption at 300–315, 400–405 and at

700–710 nm for compound F-MOF-1–5 can be observed.

The intense broad UV-vis absorption are found at 278 nm and

664 nm for F-MOF-1, at 342 nm and 651 nm for F-MOF-2, at

321 nm and 664 nm for F-MOF-3, at 309 nm and 647 nm for

F-MOF-4, and at 301 nm and 674 nm for F-MOF-5. In order to

understand the nature of the emission band, the photo-

luminescence property of free H2hfbba ligand was measured with


the observation of one weak absorption at 285 nm. In compar-

ison to the free ligand, most of the emission maxima of

F-MOFs-1 to -5 are changed which could be assigned to a joint

contribution of the intra-ligand transitions (after coordinating to

metal centers, neutral ligands may change their HOMO and

LUMO energy levels) or charge-transfer transitions between the

coordinated ligands and the metal center.

Conclusion

In this contribution we tried to understand the variables and

strategies for producing a particular kind of SBU and attempt to

identify the most likely structure that should result from the

combination of metal carboxylate with various heterocyclic

co-ligands. We successfully synthesized 5 new F-MOF structures

with a flexible dicarboxylate building block, Cu+2 and various

heterocyclic co-ligands. The structural differences between

F-MOF-1 and 5 clearly demonstrate the critical role of condi-

tions in determining the product structure from the reaction

between Cu(NO3)2$3H2O and 4,40-(hexafluoroisopropylidene)

bis(benzoic acid), (C17H10F6O4, H2hfbba) and phenanthroline.

CrystEngComm, 2010, 12, 1600–1609 | 1607


Fig. 8 Nitrogen and hydrogen adsorption isotherms for F-MOF-4.

Fig. 9 UV-vis absorption spectra for F-MOF-1–5.

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The different degree of deprotonation of H2hfbba under

appropriate conditions (i.e. change of solvent from DMF to

water and vice versa) will result in variable coordination and

hydrogen-bonding modes in the resulting crystal structure. This

work shows that the structural characteristics of auxiliary ligands

also play an important role in governing the structures of such

supramolecular complexes.

1608 | CrystEngComm, 2010, 12, 1600–1609

Acknowledgements

PP acknowledges CSIR for a project assistantship (PA-II) from

CSIR’s XIth Five Year Plan Project (NWP0022-H). CD and TP

acknowledge CSIR, New Delhi, India for fellowship support. RB

acknowledges Dr S. Sivaram, Director NCL for start-up grants

and CSIR’s XIth Five Year Plan Project (grant no: NWP0022-H)

for funding and also Dr S. Pal and Dr K. Vijaymohanan, for

their encouragement.

References

1 (a) S. R. Batten and R. Robson, in Molecular Catenanes, Rotaxanesand Knots: A Journey Through the World of Molecular Topology, ed.J.-P. Sauvage and C. Dietrich-Buchecker, Wiley-VCH, Weinheim,1999, pp. 77–105; (b) N. W. Ockwig, O. Delgado-Friederichs,M. O’Keeffe and O. M. Yaghi, Acc. Chem. Res., 2005, 38, 176; (c)R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota,R. V. Belosludov, T. C. Kobayashi, H. Sakamoto, T. Chiba,M. Takata, Y. Kawazoe and Y. Mita, Nature, 2005, 436, 238; (d)O. R. Evans and W. Lin, Acc. Chem. Res., 2002, 35, 511; (e)D. Bradshaw, J. B. Claridge, E. J. Cussen, T. J. Prior andM. J. Rosseinsky, Acc. Chem. Res., 2005, 38, 273; (f) X.-M. Chenand M.-L. Tong, Acc. Chem. Res., 2007, 40, 162; (g) R. Robson,Dalton Trans., 2008, 5113; (h) M. Du, Z.-H. Zhang, L.-F. Tang, X.-J. Zhao and S.-R. Batten, Chem.–Eur. J., 2007, 13, 2578; (i)C. Janiak, Dalton Trans., 2003, 2781; (j) S. L. James, Chem. Soc.Rev., 2003, 32, 276; (k) N. R. Champness, Dalton Trans., 2006, 877;(l) S. Natarajan and S. Mandal, Angew. Chem., Int. Ed., 2008, 47,4798–4828; (m) C. Janiak, Angew. Chem., Int. Ed. Engl., 1997, 36,1431.

2 (a) O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae,M. Eddaoudi and J. Kim, Nature, 2003, 423, 705; (b) N. L. Rosi,J. Kim, M. Eddaoudi, B. L. Chen, M. O’Keeffe and O. M. Yaghi,J. Am. Chem. Soc., 2005, 127, 1504; (c) M. O’Keeffe, M. Eddaoudi,H. Li, T. Reineke and O. M. Yaghi, J. Solid State Chem., 2000,152, 3; (d) R. Q. Snurr, J. T. Hupp and S. T. Nguyen, AIChE J.,2004, 50, 1090; (e) J. L. C. Rowsell and O. M. Yaghi, MicroporousMesoporous Mater., 2004, 73, 3; (f) S. Kitagawa, R. Kitaura andS. Noro, Angew. Chem., Int. Ed., 2004, 43, 2334; (g) U. Mueller,M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt and J. Pastre,J. Mater. Chem., 2006, 16, 626; (h) S. Kitagawa and S. Masaoka,Coord. Chem. Rev., 2003, 246, 73; (i) R.-Q. Zou, H. Sakurai,S. Han, R.-Q. Zhong and Q. Xu, J. Am. Chem. Soc., 2007, 129,8402; (j) B. J. Holliday and C. A. Mirkin, Angew. Chem., Int. Ed.,2001, 40, 2022; (k) P. J. Hagrman, D. Hagrman and J. Zubieta,Angew. Chem., Int. Ed., 1999, 38, 2638; (l) M. J. Zaworotko,Angew. Chem., Int. Ed., 2000, 39, 3052; (m) B. Moulton andM. J. Zaworotko, Chem. Rev., 2001, 101, 1629; (n) D. Bradshaw,T. J. Prior, E. J. Cussen, J. B. Claridge and M. J. Rosseinsky,J. Am. Chem. Soc., 2004, 126, 6106.

3 (a) R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa,M. O’Keeffe and O. M. Yaghi, Science, 2008, 319, 939; (b)R. Banerjee, H. Furukawa, D. Britt, C. Knobler, M. O’Keeffe andO. M. Yaghi, J. Am. Chem. Soc., 2009, 131, 3875; (c) B. Wang,A. P. Cot�e, H. Furukawa, M. O’Keeffe and O. M. Yaghi, Nature,2008, 453, 207; (d) M. Dinca, A. F. Yu and J. R. Long, J. Am.Chem. Soc., 2006, 128, 17153; (e) T. K. Maji, K. Uemura, Ho-Chol Chang, R. Matsuda and S. Kitagawa, Angew. Chem., Int. Ed.,2004, 43, 3269; (f) A. K. Cheetham and C. N. R. Rao, Science,2007, 318, 58; (g) G. F�erey, Chem. Soc. Rev., 2008, 37, 191.

4 (a) R.-Q. Zou, H. Sakurai and Q. Xu, Angew. Chem., Int. Ed., 2006,45, 2542; (b) O. Kahn, Acc. Chem. Res., 2000, 33, 647; (c) S. R. Battenand K. S. Murray, Coord. Chem. Rev., 2003, 246, 103; (d) B. Kesanliand W. Lin, Coord. Chem. Rev., 2003, 246, 305; (e) T.-T. Luo, H.-L. Tsai, S.-L. Yang, Y.-H. Liu, R. D. Yaday, C.-C. Su, C.-H. Ueng, L.-G. Lin and K.-L. Lu, Angew. Chem., Int. Ed., 2005, 44,6063; (f) X.-C. Huang, Y.-Y. Lin, J.-P. Zhang and X.-M. Chen,Angew. Chem., Int. Ed., 2006, 45, 1557; (g) B. F. Abrahams,D. J. Price and R. Robson, Angew. Chem., Int. Ed., 2006, 45, 806;(h) D.-F. Sun, S.-Q. Ma, Y.-X. Ke, D. J. Collins and H.-C. Zhou,J. Am. Chem. Soc., 2006, 128, 3896.



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7483

DView Online

5 (a) L. Pan, M. B. Sander, X. Huang, J. Li, M. Smith, E. Bittner,B. Bockrath and J. K. Johnson, J. Am. Chem. Soc., 2004, 126,1308; (b) R. Kitaura, F. Iwahori, R. Matsuda, S. Kitagawa,Y. Kubota, M. Takata and T. C. Kobayashi, Inorg. Chem., 2004,43, 6522; (c) S. Q. Liu, H. Konana, T. Kuroda-Sawa, M. Maekawa,Y. Suenaga, G. L. Ning and M. Munakata, Inorg. Chim. Acta,2005, 358, 919; (d) A. Monge, N. Snejko, E. Guti�errez-Puebla,M. Medina, C. Cascales, C. Ruiz-Valero, M. Iglesias andB. G�omez-Lor, Chem. Commun., 2005, 1291; (e) M. O. Awaleh,A. Badia and F. Brisse, Cryst. Growth Des., 2005, 5, 1897; (f)B. Chen, Y. Yang, F. Zapata, G. Qian, Y. Luo, J. Zhang andE. B. Lobkovsky, Inorg. Chem., 2006, 45, 8882; (g) F. G�andara,A. de Andr�es, B. G�omez-Lor, E. Guti�errez-Puebla, M. Iglesias,M. A. Monge, D. M. Proserpio and N. Snejko, Cryst. Growth Des.,2008, 8, 378; (h) B. V. Harbuzaru, A. Corma, F. Rey, P. Atienzar,J. L. Jord�a, H. Garcıa, D. Ananias, L. D. Carlos and J. Rocha,Angew. Chem., Int. Ed., 2008, 47, 1080; (i) R.-Q. Zhong, R.-Q. Zou,M. Du, T. Yamada, G. Maruta, S. Takeda and Q. Xu, DaltonTrans., 2008, 2346; (j) Z. Hulvey, D. S. Wragg, Z. Lin, R. E. Morrisand A. K. Cheetham, Dalton Trans., 2009, 1131; (k) H. Chun,D. N. Dybtsev, H. Kim and K. Kim, Chem.–Eur. J., 2005, 11, 3521.

6 (a) C. Yang, X. Wang and M. A. Omary, J. Am. Chem. Soc., 2007,129, 15454; (b) Z. Hulvey, E. H. L. Falcao, J. Eckert andA. K. Cheetham, J. Mater. Chem., 2009, 19, 4307.

7 (a) R.-Q. Zou, R.-Q. Zhong, M. Du, T. Kiyobayashi and Q. Xu,Chem. Commun., 2007, 2467; (b) X.-J. Jiang, S.-Z. Zhang, J.-H. Guo, X.-G. Wang, J.-S. Li and M. Du, CrystEngComm, 2009,11, 855.

8 SMART, Version 5.05; Bruker AXS, Inc.: Madison, Wisconsin, 1998.9 Bruker AXS, SAINT Software Reference Manual, Madison, WI,

1998.10 G. M. Sheldrick, (2002). SADABS (Version 2.03) and TWINABS

(Version 1.02).University of G€ottingen, Germany.11 Bruker (2004). SAINT-Plus (Version 7.03). Bruker AXS Inc.,

Madison, Wisconsin, USA.12 G. M. Sheldrick, SHELXTL NT, Program for Solution and

Refinement of Crystal Structures, version 5.1, University ofG€ottingen, G€ottingen, Germany, 1997.


13 A. L. Spek, Implemented as the PLATON procedure, A MultipurposeCrystallographic Tool, Utrecht University, Utrecht, The Netherlands,1998.

14 D. J. Tranchemontagne, J. R. Hunt and O. M. Yaghi, Tetrahedron,2008, 64, 8553.

15 (a) L. Leiserowitz, Acta Crystallogr., Sect. B: Struct. Crystallogr.Cryst. Chem., 1976, 32, 775; (b) O. Ermer and J. Lex, Angew.Chem., Int. Ed. Engl., 1987, 26, 447; (c) O. Ermer, J. Am. Chem.Soc., 1988, 110, 3747; (d) S. V. Kolotuchin, E. E. Fenlon,S. R. Wilson, C. J. Loweth and S. C. Zimmerman, Angew. Chem.,Int. Ed. Engl., 1996, 34, 2654; (e) F. H. Herbstein, ComprehensiveSupramolecular Chemistry, ed. D. D. MacNicol, F. Toda and R.Bishop, Pergamon, Oxford, 1996, vol. 6, pp. 61–83; (f)C. V. K. Sharma and M. J. Zaworotko, Chem. Commun., 1996,2655; (g) C. B. Aaker€oy, A. M. Beatty, M. Tremayne, D. M. Roweand C. C. Seaton, Cryst. Growth Des., 2001, 1, 377; (h)€O. Almarsson and M. J. Zaworotko, Chem. Commun., 2004, 1889;(i) B. R. Bhogala, P. Vishweshwar and A. Nangia, Cryst. GrowthDes., 2002, 2, 325; (j) N. Shan, A. D. Bond and W. Jones, Cryst.Eng., 2002, 5, 9; (k) A. D. Bond, Chem. Commun., 2003, 250; (l)M. Du, Z.-H. Zhang and X.-J. Zhao, Cryst. Growth Des., 2006, 6,390; (m) D. Das and G. R. Desiraju, Chem.–Asian J., 2006, 1, 231.

16 (a) G. R. Desiraju, Angew. Chem., Int. Ed. Engl., 1995, 34, 2311; (b)C. B. Aaker€oy, Acta Crystallogr., Sect. B: Struct. Sci., 1997, 53,569; (c) G. R. Desiraju, Chem. Commun., 1997, 1475; (d) A. Nangiaand G. R. Desiraju, Acta Crystallogr., Sect. A: Found. Crystallogr.,1998, 54, 934; (e) W. D. S. Motherwell, G. P. Shields andF. H. Allen, Acta Crystallogr., Sect. B: Struct. Sci., 1999, 55, 1044;(f) M. J. Zaworotko, Chem. Commun., 2001, 1; (g) A. F. Williams,Supramolecular Synthons: Encyclopedia of SupramolecularChemistry, ed. J. L. Atwood and J. Steed, 2004; (h) T. Gelbrich andM. B. Hursthouse, CrystEngComm, 2005, 7, 324; (i) G. R. Desiraju,Acc. Chem. Res., 2002, 35, 565; (j) G. R. Desiraju andR. Parthasarathy, J. Am. Chem. Soc., 1989, 111, 8725.

17 V. R. Thalladi, H.-C. Weiss, D. Blaser, R. Boese, A. Nangia andG. R. Desiraju, J. Am. Chem. Soc., 1998, 120, 9702.

18 A. W. Addison, T. N. Rao, J. Reedijk, J. V. Rijn and G. C. Verschoor,J. Chem. Soc., Dalton Trans., 1984, 1349.

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Synthesis and structural comparisons of five new fluorinated metal organic frameworks (F-MOFs

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Transcript of Synthesis and structural comparisons of five new fluorinated metal organic frameworks (F-MOFs