Structural diversity of zinc(ii) coordination polymers with octafluorobiphenyl-4,4′-dicarboxylate based on mononuclear, paddle wheel and cuboidal units

Article abstract of DOI:10.1039/c9ce00073a

We present a series of six novel Zn(ii) complexes containing anions of perfluorinated biphenyl-4,4′-dicarboxylate (oFBPDC^2?). Among them are the 0D complex [Zn(eg)₃](oFBPDC) (eg = ethylene glycol), the 1D [Zn(H₂O)(ur)(oFBPDC)] (ur = urotropine) and [Zn(CH₃OH)₂(CH₃OCH₂CH₂OH)(oFBPDC)] and the 2D layered [Zn₂(CH₃CN)₂(oFBPDC)₂]·2C₆H₆·2CH₃CN, [Zn₂(H₂O)₂(oFBPDC)₂]·4(CH₃)₂CO, [{Zn₄(μ₃-OCH₃)₄}(CH₃OH)₄(oFBPDC)₂]·[{Zn₄(μ₃-OCH₃)₄}(H₂O)(CH₃OH)₃(oFBPDC)₂]·13CH₃OH. The latter coordination polymer is built up by unique Zn₄(OCH₃)₄ cuboidal units. The complexes are characterized by single-crystal X-ray diffraction, FT-IR, elemental analysis, and TGA. Investigation of the CO₂ adsorption at 195 K on [Zn₂(CH₃CN)₂(oFBPDC)₂] and [Zn₂(H₂O)₂(oFBPDC)₂] of the layered polymeric structure revealed that they have BET surface areas of 334.8 and 150.6 m² g^?1, respectively.

Full text of DOI:10.1039/c9ce00073a

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K. A. Kovalenko, D. G. Samsonenko, A. S. Vinogradov, V. M. Karpov, V. E. Platonov and V. P. Fedin,
CrystEngComm, 2019, DOI: 10.1039/C9CE00073A.
Volume 18 Number 1 7 January 2016 Pages 1–184
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HIGHLIGHT
Tiddo J. Mooibroek, Antonio Frontera et al.
Towards design strategies for anion–π interactions in crystal engineering
rsc.li/crystengcomm

Page 1 of 21
CrystEngComm
Structural diversity of zinc(II) coordination polymers with
View Article Online
octafluorobiphenyl-4,4'-dicarboxylate based on mononucDlOeI:a10r.10,3p9/Ca9CdE0d00l7e3A
wheel and cuboidal units
1
,2
1,2
1,2
Anastasia M. Cheplakova, Konstantin A. Kovalenko, Denis G. Samsonenko, Andrey S.
3
3
3
1,2
Vinogradov, Victor M. Karpov, Vyacheslav E. Platonov, Vladimir P. Fedin
1
Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Akad. Lavrentiev Av., 630090, Novosibirsk, Russian
Federation.
2
Novosibirsk State University, 2 Pirogova Street, 630090, Novosibirsk, Russian Federation
3
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev Av., 630090, Novosibirsk,
Russian Federation.
2
−
We present a series of six novel Zn(II) complexes containing anions of perfluorinated biphenyl-4,4'-dicarboxylate (oFBPDC ).
Among them are 0D complex [Zn(eg) ](oFBPDC) (eg = ethylene glycol), 1D [Zn(H O)(ur)(oFBPDC)] (ur = urotropine) and
(CH CN) (oFBPDC) ]·2C ·2CH CN,
(µ -OCH }(H O)(CH OH) (oFBPDC)
3
2
[
Zn(CH
Zn (H O)
13CH
single-crystal X-ray diffraction, FT-IR, elemental analysis, and TGA. Investigation of CO
3
OH)
2
(CH
3
OCH
2
CH
2
OH)(oFBPDC)]
and
2D
layered
[Zn
2
3
2
2
6
H
6
3
[
2
2
2
(oFBPDC)
2
]·4(CH
3
)
2
CO, [{Zn
4
(µ
3
-OCH
3
)
4
}(CH OH)
3
4
(oFBPDC)
2
]·[{Zn
4
3
3
)
4
2
3
3
2
]
·
3
OH. The latter coordination polymer is built up by unique Zn
4
(OСH
3
)
4
cuboidal units. The complexes are characterized by
adsorption at 195 K on
2 2 2 2 2
(oFBPDC) ] and [Zn (H O) (oFBPDC) ] of layered polymeric structure revealed that they have the BET surface area
2
[Zn
2
(CH
3
CN)
2
2
of 334.8 and 150.6 m /g, respectively.
Keywords: coordination polymer, zinc(II) complexes, octafluorobiphenyl-4,4'-dicarboxylic acid
__________________________________________________________________________________
_
Introduction
Coordination polymers or metal-organic frameworks (MOFs) are an enormous class of coordination
1
,2
compounds based on both inorganic building units and organic linkers. The anions of different dicarboxylic
and polycarboxylic acids are the most widely used linkers for the design of the diverse framework structures
due to different coordination modes of each carboxylic group and their mutual arrangement in the ligand. For
3
4–7
8
instance, the most famous MOFs, like IRMOF, MIL and UiO series, are formed by anions of aromatic
carboxylic acids (terephthalic acid, naphthalenedicarboxylic, acid biphenyldicarboxylic acid, etc.).

Corresponding author
E-mail: k.a.kovalenko@niic.nsc.ru, cluster@niic.nsc.ru; Fax: +7 (383) 330 9489; Tel: +7 (383) 330 9490
1

CrystEngComm
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The replacement of H atoms with F atoms in organic compounds significantly changes their physical and
chemical properties, including polarity, polarizability, surface tension, lipophilicity, acidity and the ability to
View Article Online
9
DOI: 10.1039/C9CE00073A
form hydrogen bonds. As for metal complexes, the presence of F atoms within the structure of organic ligand
1
0
11-
often accounts for enhanced characteristics, e.g. the photoluminescence intensity, the adsorption capacity,
1
3
14
the dimensionality of the coordination polymer in case the metal complex has a polymeric structure. In
this regard, fully fluorinated biphenyldicarboxylic acid H oFBPDC is a good candidate for the construction
2
of permanently porous coordination polymers. Since H oFBPDC contains plenty of electron-withdrawing F
2
2
−
atoms, the formation of metal complexes with oFBPDC dianion can become an issue. H oFBPDC is a
2
stronger acid than non-fluorinated biphenyldicarboxylic acid, and the synthesis of metal complexes requires
2
−
mild heating or occurs even at room temperature. On the contrary, the coordination ability of oFBPDC is
much lower, so that the anion would hardly ever be able to compete with the molecules of strongly
coordinating solvents or other species for the binding to the metal cation. Thus, the coordination chemistry of
2
−
oFBPDC dianion and establishing the synthetic conditions of the formation of metal complexes are of
significant interest.
The current amount of work on this topic15–18 is still very limited in spite of the fact that the pioneering
2
−
work on oFBPDC and Cu(II) complexes was published by Miljanić in 2013 and the complexes obtained did
show intriguing properties (Table 1). For instance, activated [Cu (MeOH) (oFBPDC) ] (MOFF-1) and
2
2
2
2
[
Cu (dabco)(oFBPDC) ] (MOFF-2) with BET surface areas of 580 and 444 m /g, respectively, showed water
2 2
1
5
contact angles of 108–151°. Permanently porous perfluorinated UiO-66 and UiO-67, Zr MOFs based on
6
dianions of terephthalic and biphenyldicarboxylic acids, were shown to be considerably more Lewis acidic
than non-substituted and nitrated counterparts, which is important for catalysis and fine chemical synthesis.18
Recently we have published the paper describing the synthesis, crystal structures and adsorption properties of
1
7
six Zn complexes. Among them [Zn (dabco)(oFBPDC) ] is of special interest owing to its permanently
2
2
porous structure, selective adsorption of CO vs. N , CO vs. CH and benzene vs. cyclohexane as well as
2
2
2
4
hydrophobicity (water contact angle of 136°) and the stability in the presence of water vapors.
Herein we present the continuation of our investigation of Zn2+ + oFBPDC2− system. Certain
modifications of the previously found synthetic conditions allowed us to get six new Zn complexes which
crystal structures have been established by single crystal X-ray diffraction technique. The adsorption
properties toward CO and N of potentially porous coordination polymers have been investigated.
2
2
Experimental section
Methods
1
9
1
F and H NMR spectra were recorded on a Bruker AV 300 instrument (282.4 and 300 MHz) with
1
19
(
CD ) CO + CCl as a solvent. The chemical shifts of the H and F NMR spectra were referenced to internal
3 2 4
solvent resonances (2.05 from TMS) and C F (−162.9 ppm from CCl F). Melting point was determined on
6
6
3
2

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an Electrothermal IA9100 melting-point apparatus. FT-IR spectra of the samples in KBr pellet were recorded
−
1
on a SCIMITAR FTS 2000 spectrometer in the range of 4000–400 cm . Thermogravimetric analyses were
View Article Online
performed on a NETZSCH TG 209 F1 Iris Thermo Microbalance. Approximately 10 mgDoOfI:e1a0.c10h39s/aCm9CpE0l0e07w3Aas
placed in an aluminium crucible and then heated from room temperature up to 400 °C at the rate of
−
1
−1
1
0 °C·min under helium purge flow of 30 mL·min . Elemental analysis of fluorine-containing substances
was performed in Microanalytical Laboratory of N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry
SB RAS. N and CO isotherms of adsorption were measured volumetrically on a Quantachrome Autosorb iQ
2
2
instrument equipped with cryostat CryoCooler to adjust temperature with ±0.05 K accuracy. The samples were
preliminarily degassed in a dynamic vacuum at 150 °С for 2 h. The BET surface areas were calculated using
CO adsorption isotherms at 195 K. Pore size distributions were calculated using DFT method.
2
X-Ray Crystallography. Diffraction data for single-crystals 1–6 were obtained at 130 K on an automated
Agilent Xcalibur diffractometer equipped with an area AtlasS2 detector (graphite monochromator, λ(MoKα)
=
0.71073 Å, ω-scans). Integration, absorption correction, and determination of unit cell parameters were
1
9
performed using the CrysAlisPro program package. The structures were solved by dual space algorithm
2
0
21
(
SHELXT ) and refined by the full-matrix least squares technique (SHELXL ) in the anisotropic
approximation (except hydrogen atoms). Positions of hydrogen atoms of organic ligands were calculated
geometrically and refined in the riding model. Structure 6 contains a large void volume occupied by highly
disordered solvent guest methanol molecules, which could not be refined as a set of discrete atoms. The final
2
2
−
3
composition of compound 6 was defined according to PLATON/SQUEEZE procedure (592 e in 1792 Å ).
The crystallographic data and details of the structure refinements are summarized in Table 2. CCDC 1879950-
1
879955 contain the supplementary crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Center at https://www.ccdc.cam.ac.uk/structures/.
Synthesis of H oFBPDC and complexes 1-6
2
1
7
Zn(OH) was obtained in the same way as in our previous paper. Acetone was dried over molecular
2
sieves 3 Å (Sigma Aldrich). All other chemicals and solvents were commercially available and used as
received without further purification. Octafluorobiphenyl-4,4'-dicarboxylic acid was synthesized via acid
hydrolysis of diethyl octafluorobiphenyl-4,4'-dicarboxylate. The latter was prepared by the reaction of
1
6
organozinc compound, obtained from ethyl pentafluorobenzoate, with anhydrous CuCl (Scheme S1).
2
Synthesis of octafluorobiphenyl-4,4'-dicarboxylic acid (H oFBPDC). Diethyl octafluorobiphenyl-4,4'-
2
dicarboxylate (17.29 g, 39.1 mmol), concentrated sulphuric acid (34 ml), glacial acetic acid (100 ml), and
water (34 ml) were heated under reflux for 45 h. Then, the reaction mixture was cooled down and evaporated
in vacuum. The solid was filtered off, washed with cold water, and dried to a constant weight at 120 °C to
1
give pure octafluorobiphenyl-4,4'-dicarboxylic acid (14.33 g, 37.1 mmol, yield 95%). m.p. 320-322 °C. H
1
9
NMR spectrum [(CD ) CO + CСl ], δ, ppm: 10.07 br. s (2H, COOH). F NMR spectrum [(CD ) CO + CСl ],
3
2
4
3 2
4
3

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δ, ppm: −137.4 m (4F), −139.1 m (4F). Found, %: C 43.29; H 0.42; F 39.28; calculated for C H F O , %: C
1
4
2
8
4
4
3.55; H 0.52; F 39.36.
Synthesis of [Zn(eg) ](oFBPDC) (1). The mixture of Zn(OH) prepared from Zn(NO ) ·6H O (0.040 g,
View Article Online
DOI: 10.1039/C9CE00073A
3
2
3 2
2
0
.136 mmol), H oFBPDC (0.050 g, 0.128 mmol) was dissolved in 4.0 mL of ethylene glycol (eg) and placed
2
in a 4.5 mL screw cap vial and thoroughly sonicated. Then the vial was heated in the oven at 40 °C for 48 h
to obtain a crystalline precipitate. The precipitate was filtered off on the glass frit, washed with eg and dried
in air. Yield 0.050 g (60%). TGA profile shows a weight loss of ca. 30% by 280 °C which is attributed to the
loss of 3 eg molecules per one Zn atom. Found, %: C 37.62, H 2.61, F 23.96; calculated for C H F O Zn,
2
0
18
8
10
−
1
%
: C 37.79, H 2.85, F 23.91. FT-IR, ν/cm : 3445 (s, br), 2953 (s), 2884 (m), 1619 (s), 1560 (s), 1469 (s),
1
6
454 (s), 1370 (s), 1263 (m), 1202 (w), 1082 (s), 1040 (s), 1007 (s), 976 (s), 880 (m), 837 (s), 774 (s), 723 (s),
97 (m), 406 (m).
Synthesis of [Zn(H O)(ur)(oFBPDC)] (2). The single crystals of 2 suitable for X-ray diffraction analysis
2
were found in the reaction mixture containing Zn(OH) prepared from Zn(NO ) ·6H O (0.010g, 0.034 mmol),
2
3 2
2
H oFBPDC (0.013 g, 0.032 mmol), urotropine (0.0047 g, 0.034 mmol) and 1.5 mL of EtOH after its
2
ultrasonication, prolonged dwelling (ca. 3 months) at room temperature and further heating up to 60 °C for 1
day. Structure and the chemical formula of 2 were determined by single-crystal X-ray diffraction.
Synthesis of [Zn(CH OH) (CH OCH CH OH)(oFBPDC)] (3). The mixture of Zn(OH) prepared from
3
2
3
2
2
2
Zn(NO ) ·6H O (0.010g, 0.034 mmol), H oFBPDC (0.013 g, 0.032 mmol) was dissolved in the mixture of
3
2
2
2
CH OH and 2-methoxyethanol (v:v = 1:1, 3 mL in total), placed in a 4.5 mL screw cap vial and thoroughly
3
sonicated. Then the vial was heated in the oven at 40 °C for 72 h to obtain a crystalline precipitate. Structure
and the chemical formula of 3 were determined by single-crystal X-ray diffraction.
Synthesis of [Zn (CH CN) (oFBPDC) ]∙2C H ·2CH CN (4). Zn(NO ) ·6H O (0.200 g, 0.66 mmol),
2
3
2
2
6
6
3
3 2
2
H oFBPDC (0.250 g, 0.64 mmol) were dissolved in the mixture containing 8.0 mL of CH CN and 4.0 mL
2
3
C H . The solution was placed in a 20 mL screw cap vial and heated at 80 °C for 48 h. The solid obtained was
6
6
filtered off, washed with CH CN and dried in air. Yield 0.090 g (25%). Upon the isolation of 4 from the
3
mother liquor it loses guest molecules, and the final composition is [Zn (CH CN) (oFBPDC) ]
2
3
2
2
∙
0.3C H ·1.6CH CN. Found, %: C 40.55, H 1.09, N 4.60, F 27.96; calculated for C H F N O Zn , %: C
6 6 3 37 12.6 16 3.6 8 2
−
1
4
2
9
1.52, H 1.19, N 4,71, F 28.40. FT-IR, ν/cm : 3511 (w), 3420 (w), 3358 (w), 3282 (w), 2361 (w), 2322 (w),
295 (w), 2258 (w), 1694 (s), 1656 (s), 1616 (s), 1591 (s), 1470 (s), 1403 (s), 1251 (w), 1133 (w), 1000 (s),
78 (s), 816 (s), 768 (s), 718 (s), 690 (w), 678 (w), 655 (w), 597 (w), 517 (w), 479 (w), 440 (w).
Synthesis of [Zn (H O) (oFBPDC) ]∙4(CH ) CO (5). The mixture of Zn(OH) prepared from
2
2
2
2
3 2
2
Zn(NO ) ·6H O (0.010g, 0.034 mmol), H oFBPDC (0.013 g, 0.032 mmol), 3.0 mL of acetone and 25 μL (1.4
3
2
2
2
mmol) of distilled water was placed in a 4.5 mL screw cap vial without ultrasonication. When the vial was
heated in the oven at 40 °C for 10 days, colourless block crystals were obtained. The crystals were filtered off,
washed with acetone and dried in air. Yield 0.0075 g (45%). Upon the isolation of 5 from the mother liquor it
4

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loses guest molecules of acetone and the final composition is [Zn (H O) (oFBPDC) ]∙1.3(CH ) CO. Found,
2
2
2
2
3 2
−
1
%
: C 37.56, H 1.18, F 29.70; calculated for C31.9H11.8F O Zn , %: C 37.91, H 1.18, F 30.08. FT-IR, ν/cm :
16 11.3 2
View Article Online
3
7
576 (s, br), 1617 (s), 1560 (w), 1469 (s), 1452 (s), 1370 (s), 1264 (w), 1006 (s), 977 (s)D,O8I:3107.10(3w9/)C,98CE10700(7w3A),
74 (s), 722 (s), 697 (w), 406 (w).
Synthesis of
[
{Zn (µ -OCH ) }(CH OH) (oFBPDC) ]∙[{Zn (µ -OCH ) }(H O)(CH OH) (oFBPDC) ]∙13CH OH
4 3 3 4 3 4 2 4 3 3 4 2 3 3 2 3
(
6). The mixture of Zn(OH) prepared from Zn(NO ) ·6H O (0.010g, 0.034 mmol), H oFBPDC (0.010 g,
2 3 2 2 2
0
.026 mmol), 2.9 mL of CH OH and 100 μL (1.80 mmol) of ethylene glycol was placed in a 4.5 mL screw
3
cap vial and thoroughly sonicated. Then the vial was heated in the oven at 60 °C for 3 weeks. After that, the
reaction mixture represents an amorphous solid and a few single crystals suitable for X-ray diffraction
analysis. Structure and the chemical formula of 6 were determined by single-crystal X-ray diffraction. FT-IR,
−
1
ν/cm : 3400 (s, br), 2953 (w), 2837 (w), 2384 (w), 1620 (s), 1468 (s), 1389 (s), 1252 (w), 1132 (w), 1002 (s),
9
78 (s), 843 (w), 816 (w), 772 (s), 719 (s), 513 (w).
Results and discussion
The majority of already described Zn(II)17 and Cu(II)15 complexes with oFBPDC2− dianion were
synthesized in methanol or its mixtures with DMF where methanol is the major component of the mixture.
We tried other alcohols, polyols, and their derivatives, mixtures with methanol as well as CH CN and acetone
3
and check whether these solvents are favourable for the formation of Zn complexes.
Synthesis and crystal structure of complex 1
Vicinal diols, e.g. ethylene glycol (eg), can act not only as a viscous polar solvent but also as a chelating
ligand producing 1D and 2D coordination polymers with non-fluorinated23–25 and perfluorinated
2
6
carboxylates . Nevertheless, the mixture of Zn(OH) and H oFBPDC completely dissolves in eg, and the
2
2
heating of this solution at 40 °C leads to the formation of the non-polymeric complex [Zn(eg) ](oFBPDC) (1).
3
Each Zn(II) cation is in a distorted octahedral coordination environment consisting of six O atoms of three eg
2
+
molecules, which produce [Zn(eg) ] cation. Zn–O distances are in the range 2.061(4)–2.124(4) Å. The
3
2
−
2−
oFBPDC anion is not bounded to Zn and act as a counter-ion in this salt. The carboxylic group of oFBPDC
takes part in multiple hydrogen bonding interactions with H atoms of coordinated eg to form a supramolecular
chain running along [−103] direction. O…O distances are 2.564–2.679 Å. The chains are stacked along c axis
to form the hydrogen-bonded layer parallel to the ac plane (Fig. 1). The layers are stacked in ABAB fashion
along the b axis.
5

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Page 6 of 21
View Article Online
DOI: 10.1039/C9CE00073A
Fig. 1. Fragment of hydrogen-bonded layer in the structure 1. Hydrogen bonds are shown with dashed lines. Hydrogen
atoms are omitted for clarity.
Syntheses and crystal structures of complexes 2-3
The mixture of Zn(OH) , H oFBPDC and ur in 1:1:1 molar ratio reacts in methanol and gave the complex
2
2
1
7
[
Zn(CH OH) (ur)(oFBPDC)] of the chain-like polymeric structure. In this complex, each Zn(II) cation is in
3 3
a distorted octahedral coordination environment, consisting of two O atoms of carboxylate, one N atom of
terminal ur and three O atoms of CH OH molecules. Meanwhile, the same mixture of H oFBPDC, ur, and the
3
2
metal source in ethanol leads to the zigzag chain-like polymer. According to the X-ray crystallography, it has
the chemical formula [Zn(H O)(ur)(oFBPDC)] (2). In the compound 2, each Zn(II) cation is in a distorted
2
tetrahedral coordination environment, which is presented by one N atom of terminal ur, two O atoms of
dicarboxylate and one O atom of a water molecule (Fig. 2a). Zn–O distances are 1.950(4)–1.979(4) Å, Zn–N
distance is 2.037(7) Å. The zigzag chains stack along b axis to form layers parallel to bc plane. Then the layers
are stacked along the a axis to form double-layer crystal packing (Fig. S4). Careful inspection of interatomic
distances revealed the absence of any hydrogen bonding interaction in the crystal structure of 2.
Methyl cellosolve (2-methoxyethanol), the methylated derivative of ethylene glycol, is often used as a
solvent for the synthesis of organic and coordination compounds. Heating of Zn(OH) and H oFBPDC in the
2
2
mixture of CH OH and 2-methoxyethanol (v:v = 1:1) at 40 °C gives also a chain-like coordination polymer
3
[
Zn(CH OH) (CH OCH CH OH)(oFBPDC)] (3). Zn(II) cations are in a distorted octahedral environment
3 2 3 2 2
2
−
consisting of two O atoms of oFBPDC , two O atoms of CH OH molecules and two O atoms of 2-
3
6

Page 7 of 21
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methoxyethanol. Zn–O distances are 2.0375(13)-2.288(2) Å. In this case, 2-methoxyethanol acts as a chelating
ligand. Coordinated CH OH and 2-methoxyethanol molecules are disordered over two orientations (Fig. S5).
3
View Article Online
2
−
DOI: 10.1039/C9CE00073A
Each carboxylic group is coordinated in a monodentate fashion, oFBPDC dianion acts as a bridging ligand
connecting the adjacent Zn(II) cations to form almost linear chains (Fig. 2b). These chains form a
supramolecular layer in bc plane due to hydrogen bonding interactions between non-coordinated O atom of
carboxylic group of one chain and H atom of coordinated methanol molecule of the adjacent chain. O…O
distances are 2.612–2.684 Å. The supramolecular layers stack along c axis producing double-layer crystal
packing.
a)
7

CrystEngComm
Page 8 of 21
b)
Fig. 2. Fragments of the polymeric chains a) in the structure 2; b) in the structure 3 (major orientation of coordinated
View Article Online
methanol and 2-methoxyethanol is shown). Hydrogen atoms are omitted for clarity. Hydrogen b
D
o
O
n
I:
d
10
s
.1
a
0
r
3
e
9/
s
C
h
9
o
CE
w
0
n
00
with
73
A
dashed lines.
Syntheses and crystal structures of complexes 4-5
A dinuclear [M (CO ) L ] paddle wheel building unit appeared to be a typical motif in Zn coordination
2
2 2 2
polymers with oFBPDC2− dianion. The paddle wheel unit is found in complexes
1
7
[
Zn (CH CONH ) (oFBPDC) ]·3CH CN and [Zn (dabco)(oFBPDC) ]·4.5CH OH as well as in complexes
2 3 2 2 2 3 2 2 3
[
Zn (CH CN) (oFBPDC) ]·2C H ·2CH CN (4) and [Zn (H O) (oFBPDC) ]∙4(CH ) CO (5). All of them
2
3
2
2
6
6
3
2
2
2
2
3 2
2
−
have layers formed by Zn paddle wheel units and oFBPDC dianions (Fig. 3). The differences between the
layered structures 4 and 5 are in the nature of apical ligands L and the deviation from the ideal square grid
network (Fig. 3). Zn–O distances are 2.0286(12)–2.0468(12) Å, Zn–N distance in 4 is 2.0185(15) Å, Zn–OH2
distance in 5 is 1.952(4) Å. The compound 4 was obtained by a reaction between Zn(NO ) ·6H O and
3
2
2
H oFBPDC in the mixture of solvents CH CN/C H (v:v = 2:1) at 80 °C. Interestingly, 4 formed as large
2
3
6
6
single crystals of a few millimeters in size (Fig. S6). It was expected that benzene could take part in π-π
interactions with fluorine-substituted phenyl rings27,28 of oFBPDC linkers, playing the role of the template and
leading to a coordination polymer with the different crystal structure under the same synthetic conditions.
Indeed, owing to rapid crystallization of 4 there was no acid-catalyzed hydrolysis, and CH CN is coordinated
3
to Zn(II) cations in contrast to CH CONH in the synthesis of [Zn (CH CONH ) (oFBPDC) ]·3CH CN. Guest
3
2
2
3
2 2
2
3
molecules of benzene take part in π-π interactions with fluorine substituted phenyl rings. The shortest С…C
distances are 3.618 Å and 3.679 Å (Fig. 3a). The layered coordination polymer 4 can be a perfect starting
material for the synthesis of porous coordination polymers of the 3D structure via heterogeneous pillar
2
9
insertion strategy since Zn(II) cations are coordinated by weakly bounded and easily displaced CH CN
3
molecules.
The compound [Zn (H O) (oFBPDC) ]·4(CH ) CO (5) has a very similar layered structure (Fig. 3b). For
2
2
2
2
3 2
the first time, the single crystals of 5 were found in the mixture of freshly prepared Zn(OH) and H oFBPDC
2
2
in acetone after ultrasonication and ca. 1 month of dwelling at room temperature. Afterwards, the procedure
was optimized in order to get an only crystalline precipitate. The optimized procedure implies the addition of
a small amount of water and heating up to 40 °C. In this complex, apical ligand is water disordered over two
orientation (Fig. S9). According to X-ray crystallography data, there are four guest molecules of acetone per
Zn unit, which are linked to coordinated water molecules via hydrogen bonding (Fig 5a, S9). O…O distances
2
are 2.646 and 2.723 Å. The metal-organic polymeric layers in both 4 and 5 are packed in a double-layer fashion
with the apical ligands pointing in the square openings of the adjacent layer (Fig. S7, S10, S11).
8

Page 9 of 21
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DOI: 10.1039/C9CE00073A
a)
9

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Page 10 of 21
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DOI: 10.1039/C9CE00073A
b)
Fig. 3. The structure of the metal-organic polymeric layer a) in complex 4, b) in complex 5. Hydrogen atoms in structure
are omitted for clarity. The shortest C…C distances between guest molecules of benzene and oFBPDC linker in
5
structure 4 and hydrogen bonds between coordinated water molecules and acetone guest molecules in structure 5 are
shown with dashed lines.
Synthesis and crystal structure of complex 6
As it was shown above, the solvent often plays the crucial role in the formation for Zn(II) perfluorinated
carboxylates. Using significant amounts of chelating solvents like ethylene glycol and 2-methoxyethanol leads
to 0D and 1D structures 1 and 2, respectively. On the other hand, synthesis in pure methanol results in the
1
7
formation of previously described [Zn(CH OH) (oFBPDC)] of the layered polymeric structure.
3
3
Interestingly, prolonged heating (ca. 1 month) at 60 °C of Zn(OH) , H oFBPDC in CH OH with a small
2
2
3
additive of eg gives an unidentified amorphous precipitate together with crystals of unusual complex [{Zn (µ -
4
3
OCH ) }(CH OH) (oFBPDC) ]·[{Zn (µ -OCH ) }(H O)(CH OH) (oFBPDC) ]·13CH OH (6). Compound 6
3
4
3
4
2
4
3
3 4
2
3
3
2
3
1
0

Page 11 of 21
CrystEngComm
has a layered polymeric structure with a very unusual {Zn (μ -OCH ) } cuboidal building unit. Zn(II) and O
4
3
3 4
−
atoms are located in the vertices of a slightly distorted cube, each CH O -group acts as a μ -lidand. The unit
3
3
View Article Online
DOI: 1 03 0. 1 –0 33 29 /C9CE00073A
is typical for organometallic compounds, obtained by the controlled oxidation of zinc alkyls,
but not for
Zn coordination polymers. To the best of our knowledge, compound 6 is the first example of Zn coordination
polymer based on {Zn (μ -OCH ) } units. In the structure 6, there are two distinct cuboidal units, which are
4
3
3 4
different in the ligands completing the coordination environment of Zn(II). The unit of the first type comprises
[
(
[
Zn (μ -OCH ) (CH OH) (RCO ) ] block, in which all four Zn(II) cations are coordinated by four CH OH
4 3 3 4 3 4 2 4 3
Fig. 4a). In the unit of the second type, one of the terminal methanol molecules is substituted by aqua-ligand:
Zn (μ -OCH ) (H O)(CH OH) (RCO ) ] (Fig. 4b). Each carboxylic group links two adjacent Zn(II) cations
4
3
3 4
2
3
3
2 4
in one cuboidal unit. Zn–OCH distances are 2.028(10)–2.139(10) Å, Zn–OCO distances range from
3
2
−
2
.066(7) Å to 2.168(7) Å. Perfluorinated biphenyl moiety of oFBPDC linker connects cuboidal building
units in two perpendicular directions producing a square grid layer (Fig. 5). Each layer contains the cuboidal
2
−
units of only one type. There is a system of hydrogen bonding interactions between O atoms of oFBPDC ,
coordinated methanol, and water molecules. O…O distances are 2.676–2.836 Å. These interactions make
adjacent Zn (OCH ) units to be situated close to each other (Fig. 6, S13). The spatial arrangement of the
4
3 4
layers is described as a four-layer packing (Fig. 6). The crystal structure has the system of isolated helical
channels, which are presumably filled by highly disordered solvent guest molecules (Fig. S14). According to
the PLATON/SQUEEZE estimation, there are 13 methanol guest molecules by formula unit of the compound
6
.
a)
b)
Fig. 4. Zn O cuboidal units in the crystal structure of 6: a) [{Zn (μ -OCH ) }(CH OH) (RCO ) ], b) [{Zn (μ -
4
4
4
3
3 4
3
4
2 4
4
3
OCH ) }(H O)(CH OH) (RCO ) ].
3
4
2
3
3
2 4
1
1

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Page 12 of 21
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DOI: 10.1039/C9CE00073A
Fig. 5. The structure of the metal-organic polymeric layer in complex 6. Hydrogen atoms are omitted for clarity.
1
2

Page 13 of 21
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DOI: 10.1039/C9CE00073A
Fig. 6. Packing of the layers in 6. View along the a axis. Hydrogen atoms are omitted for clarity.
Guest removal and thermal stability of 4 and 5
Complexes 4–5 contain a lot of solvent guest molecules and have similar layered crystal structures. The
results
of
elemental
CHNF
analysis
match
well
with
chemical
formulas
[
Zn (CH CN) (oFBPDC) ]·0.3C H ·1.6CH CN for 4 and [Zn (H O) (oFBPDC) ]·1.3(CH ) CO for 5. These
2
3
2
2
6
6
3
2
2
2
2
3 2
formulas are in a good agreement with the composition revealed by single crystal X-ray diffraction and a
partial loss of guest molecules while the isolation of these solids from the mother liquor. The amounts of guest
molecules are also confirmed by thermal analysis data (Fig. S17). TG curve of 4 shows the loss of C H and
6
6
CH CN guest molecules (ca. 8%) and one of the coordinated CH CN ligand (ca. 4%) in the temperature region
3
3
9
0–150 °C. The second stage up to 215 °C corresponding to the loss of the second coordinated CH CN ligand
3
results in the formation of [Zn (oFBPDC) ]. The following step in the temperature range 240–400 °C is
2
2
attributed to the coordination polymer degradation with the formation of zinc- and amorphous carbon-
containing products. The mass loss of compound 5 is ca. 8.5% up to 160 °C which corresponds to the release
of 1.4 molecules of acetone. Compound 5 does not undergo further mass loss up to 280 °C, followed by the
coordination polymer degradation with the formation of amorphous products.
For further gas adsorption measurements we carried out the activation of synthesized frameworks in high
vacuum at 150 °C as the optimal temperature to remove all guest molecules as well as weakly coordinated
CH CN ligands in polymer 4. The FT-IR spectra (Fig. S18) confirm the successful guest removal. In FT-IR
3
−
1
spectra of activated 4 the peaks of CN valence vibrations in 2500–2300 cm range completely disappear
confirming removal of both guest and coordinated CH CN molecules. A broad peak in the region of 3600–
3
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3

CrystEngComm
Page 14 of 21
–
1
3
100 cm confirms the presence of coordinated water molecules in the activated compound 5, while slight
changes of ν(CO) line profiles is attributed to the removal of acetone guest molecules.
View Article Online
DOI: 10.1039/C9CE00073A
Adsorption properties of coordination polymers 4 and 5
The analysis of crystal packing of coordination polymers 4 and 5 allows us to suggest that they should
demonstrate permanent porosity after complete removal of guest molecules. Indeed, the accessible void
volumes could be estimated by Mercury software routine as 30.5% and 35.5% for 4 and 5, respectively.
Nevertheless, activated 5 does not adsorb N in a measurable amount, and we have failed to measure this
2
3
isotherm, while N uptake of 4 is only ca. 16 cm /g (Fig. 7). It should be the consequence of narrow pore
2
necks which do not allow N molecules to penetrate into pores and channels. Unlike N , CO has a smaller
2
2
2
kinetic diameter and a quadrupole moment. Therefore, CO adsorption at 195 K is often used to determine the
2
textural properties of such solids instead of N adsorption. According to the official IUPAC classification, the
2
3
isotherms of CO adsorption for both 4 and 5 belong to I type. CO uptake of 4 (89 cm /g) is slightly less than
2
2
3
the estimated volume (110 cm /g), while complex 5 demonstrates lower CO uptake, though the estimated
2
accessible void volume is larger than for 4. Such discrepancy for 5 can be explained by significant changes in
the packing of the polymeric layers upon the removal of all acetone guest molecules, which could involve
hydrogen bonding interaction between coordinated water molecules of adjacent layers of the same type (Fig.
2
S11). The BET surface areas calculated on the basis of the isotherms of CO adsorption are 334.8 m /g and
2
2
3
3
1
50.6 m /g, pore volumes are 0.187 cm /g and 0.094 cm /g for 4 and 5, respectively. Pore size distribution
curves were calculated using DFT approach (Fig. S19). Pore diameters obtained are in agreement with the
estimation made on the basis of the single crystal data.
1
4

Page 15 of 21
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4
, CO , 195 K
5, CO , 195 K
4, N , 77 K
2
2
2
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
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DOI: 10.1039/C9CE00073A
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Relative pressure, P/P0
Fig. 7. Isotherms of adsorption on 4 and 5.
Despite moderate surface areas and pore volumes both compounds 4 and 5 demonstrate high selectivity
of adsorption of CO over N . It should be noted that the similar behaviour was observed earlier for compound
2
2
1
7
[
Zn (CH CONH ) (oFBPDC) ] with almost the same layered structure.
2 3 2 2 2
Conclusions
Perfluorination of an organic carboxylate ligand results in its distinctive electronic and acidic properties
and the coordination ability. The synthesis of perfluorinated coordination polymers occurs at moderate
temperature in comparison with many other MOFs based on non-fluorinated aromatic carboxylates. The
2
−
literature data together with our present experiments have shown that the oFBPDC metal complexes do form
in a weakly coordinating solvent (CH CN, acetone, alcohols, THF) or its mixtures with a small additive of
3
coordinating solvent (DMF, water, eg) or extra N-donor ligand (ur, dabco, bpy).
Different coordination numbers of Zn(II) cation and ability to form secondary building units of diverse
2
−
structure allow us to get six new metal complexes containing oFBPDC . Thus, ethylene glycol appeared to
be a strongly coordinating solvent, and the heating of the reaction mixture results in complex
[
Zn(eg) ](oFBPDC) of non-polymeric structure, while the reaction in the mixture of CH OH and 2-
3
3
methoxyethanol produces chain-like polymer [Zn(CH OH) (CH OCH CH OH)(oFBPDC)]. In contrast to the
3
2
3
2
2
reaction of Zn(OH) , H oFBPDC and ur in methanol giving [Zn(CH OH) (ur)(oFBPDC)] with octahedral
2
2
3
3
1
5

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Page 16 of 21
coordination of Zn(II) cations, the same reaction in ethanol gives [Zn(H O)(ur)(oFBPDC)] with CN=4.
2
Dinuclear [Zn (CO ) L ] paddle wheel unit is found in the layered coordination polymers
2
2 2 2
View Article Online
DOI: 10.1039/C9CE00073A
[
Zn (CH CN) (oFBPDC) ]·2C H ·2CH CN and [Zn (H O) (oFBPDC) ]·4(CH ) CO with CH CN and H O
2 3 2 2 6 6 3 2 2 2 2 3 2 3 2
as apical ligands, respectively. Finally, prolonged heating of the mixture of Zn(OH) , H oFBPDC and ethylene
2
2
glycol in methanol gives the polymer of layered structure based on unique for coordination polymers
Zn (OCH ) cuboidal units. Heating of the layered [Zn (CH CN) (oFBPDC) ]·2C H ·2CH CN and
4
3 4
2
3
2
2
6
6
3
[
Zn (H O) (oFBPDC) ]·4(CH ) CO in vacuum results in the removal of volatile guest molecules and lead to
2 2 2 2 3 2
permanently porous solids. The BET surface areas calculated on the basis of isotherms of CO adsorption at
2
2
1
95 K are 334.8 and 150.6 m /g, respectively.
Conflicts of interest
There are no conflicts to declare.
Acknowledgment
This work was supported by the Russian Foundation for Basic Research (Grant No. 17-03-00027). The
authors would like to acknowledge the Multi-Access Chemical Service Center SB RAS for spectral and
analytical measurements.
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1
7

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Page 18 of 21
Table 1. The summary of the synthetic conditions for the preparation of oFBPDC-containing metal complexes.
Metal
Chemical formula
Starting materials
Synthetic conditions
OH/DMF/H O (v:v:v =18:1:1), 40 °C,
3 2
Dimensi
onality
2D
Ref
1
1
5
5
Cu
[Cu (CH OH) (oFBPDC) ]·0.5CH OH (MOFF-1)
Cu(NO ) ·2.5H O, H oFBPDC, 1:1
CH
days
2
3
2
2
3
3 2
2
2
4
[
Cu (dabco)(oFBPDC) ] (MOFF-2)
Cu(NO ) ·2.5H O, H oFBPDC,
CH OH/DMF/H O (v:v:v =20:3.33:1), 60 °C,
3D
2
2
3 2
2
2
3
2
dabco
:2:1
Zn(OH) , H oFBPDC, 1:1
2 days
2
Zn
[Zn(eg) ](oFBPDC)
eg, 40 °C, 48 h
0D
1D
1D
This
work
This
work
This
work
3
2
2
[
Zn(H O)(ur)(oFBPDC)]
Zn(OH) , H oFBPDC, ur, 1:1:1
C H OH, 20–60 °C, 3 months
2 5
2
2
2
[
Zn(CH OH) (CH OCH CH OH)(oFBPDC)]
Zn(OH) , H oFBPDC, 1:1
CH OH/ 2-methoxyethanol (v:v = 1:1),
3
2
3
2
2
2
2
3
4
0 °C, 72 h
1
7
[
Zn(CH OH) (ur)(oFBPDC)]
Zn(OH) , H oFBPDC, ur, 1:1:1
CH OH, 40 °C, 24 h
1D
2D
3
3
2
2
3
1
7
[
Zn (oFBPDC) (CH CONH ) ]·3CH CN
Zn(NO ) ·6H O, H oFBPDC,
CH CN, 80 °C, 40 h
2
2
3
2 2
3
3 2
2
2
3
CH CONH 1:1:1
3
2
1
7
[
Zn(CH OH) (oFBPDC)]
Zn(OH) , H oFBPDC, 1:1
CH OH, 60 °C, 24 h
2D
2D
3
3
2
2
3
[
Zn (CH CN) (oFBPDC) ]·2C H ·2CH CN
Zn(NO
3
)
2
·6H
2
O, H
2
oFBPDC, 1:1
CH
acetone, H
CH OH/eg (v:v = 30:1), 60 °C, 3 weeks
3
CN/C
6
H
6
(v:v = 2:1), 80 °C, 48 h
This
work
This
work
This
work
2
3
2
2
6
6
3
[
Zn (H O) (oFBPDC) ]·4(CH ) CO
Zn(OH)
Zn(OH)
2
2
, H
, H
2
2
oFBPDC, 1:1
oFBPDC
2
O (v:v = 2:1), 40 °C, 10 days
2D
2D
2
2
2
2
3 2
[
[
[
[
(
{Zn (µ -OCH ) }(CH OH) (oFBPDC) ]·
3
4
3
3 4
3
4
2
{Zn (µ -OCH ) }(H O)(CH OH) (oFBPDC) ]·13CH OH
4
3
3 4
2
3
3
2
3
1
1
1
1
1
7
7
7
6
6
Zn (H O) (thf) (oFBPDC) ]·3.5H O·2.5THF
Zn(OH) , H oFBPDC, 1:1
THF, 40 °C, 6 days
3D
3D
3D
2
2
1.5
1.5
2
2
2
2
Zn (oFBPDC) dabco]·4.5CH OH
Zn(OH) , H oFBPDC, dabco, 2:2:1
CH OH, 80 °C, 48 h
2
2
3
2
2
3
H bipy)[Zn (bipy)(oFBPDC) ]
Zn(OH) , H oFBPDC, bpy, 2:3:2
H O, 70 °C, 72 h
2
2
2
3
2
2
Ln = [Ln (H O) (oFBPDC) ]·3H O
Tb, Eu [Ln (phen) (oFBPDC) ]·2H O
Ln(OH) , H oFBPDC, 2:3
dissolution in water at room temperature with
further precipitation by adding
2
2
4
3
2
3
2
Ln(OH) , H oFBPDC, phen∙H O,
3 2 2
2
2
3
2
2
:3:2
acetone/CH
OH mixture (v:v = 3:1)
3
1
8
Zr
[Zr O (OH) (oFBPDC) ((OH)(OH ))3.46]
ZrOCl ∙8H O, H oFBPDC, 1:1
THF/HClconc. (v:v = 96:1), 80 ºC, 24 h
3D
6
4
4
4.27
2
2
2
2
1
8

Page 19 of 21
CrystEngComm
Table 2. Crystal data and structure refinement for 1–6.
Identification code
1
2
3
4
5
6
Empirical formula
M, g/mol
Crystal system
Space group
a, Å
C H F O Zn
C H F N O Zn
C H F O Zn
C H F N O Zn
C H F O Zn
C H F O Zn
8
2
0
18
8
10
20 14
8
4
5
19 16
8
8
24 12
8
2
4
40 28 16 14
2
84 106 32 45
635.71
607.72
589.69
609.73
1167.36
2966.64
Monoclinic
I2
Monoclinic
Monoclinic
Monoclinic
C2/c
Orthorhombic
I222
Monoclinic
P21
P2 /c
P2 /c
1
1
12.6244(3)
15.2868(4)
38.1764(8)
14.9250(12)
5.4485(4)
13.3346(4)
15.4645(4)
10.9486(3)
19.7538(4)
10.5400(2)
23.0099(5)
10.2288(5)
15.2173(7)
15.2087(6)
17.6709(4)
18.1755(7)
17.7050(4)
b, Å
c, Å
27.4123(15)
α, deg.
β, deg.
97.201(2)
101.413(6)
94.460(3)
90.091(2)
91.349(2)
γ, deg.
V, Å3
7309.4(3)
12
2185.1(3)
4
2250.91(11)
4
4790.79(18)
8
2367.31(18)
2
5684.9(3
2
Z
D(calc.), g/cm3
μ, mm−1
F(000)
1.733
1.847
1.236
1216
1.740
1.691
1.123
2432
1.638
1.139
1168
1.733
1.795
2996
1.123
1.201
3840
1184
Crystal size, mm
0.31 × 0.14 × 0.13
3.30–28.45
0.66 × 0.14 × 0.02
3.42–25.35
0.23 × 0.16 × 0.11
3.34–29.06
0.34 × 0.18 × 0.12
3.44–28.88
0.25 × 0.13 × 0.05
3.60–25.68
0.27 × 0.22 × 0.10
3.22–25.68
θ range for data collection,
deg.
Index ranges
−16 ≤ h ≤ 13,
−17 ≤ h ≤ 15,
−6 ≤ k ≤ 5,
−33 ≤ l ≤ 27
−17 ≤ h ≤ 16,
−20 ≤ k ≤ 20,
−14 ≤ l ≤ 14
−26 ≤ h ≤ 26,
−12 ≤ k ≤ 14,
−29 ≤ l ≤ 29
−9 ≤ h ≤ 12,
−17 ≤ k ≤ 18,
−17 ≤ l ≤ 18
−21 ≤ h ≤ 21,
−22 ≤ k ≤ 22,
−21 ≤ l ≤ 21
−
−
19 ≤ k ≤ 15,
47 ≤ l ≤ 50
Reflections collected /
independent
20127 / 12281
8828 / 3969
35566 / 5531
12581 / 5279
3739 / 2123
33516 / 19128
Rint
0.0136
0.0307
3168
0.0258
4678
0.0180
4696
0.0199
2083
0.0245
Reflections with I > 2σ(I)
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
10116
17906
1.044
1.050
1.044
1.047
1.034
1.032
R1 = 0.0284;
R1 = 0.0730;
R1 = 0.0307;
R1 = 0.0264;
R1 = 0.0314;
R1 = 0.0670;
wR = 0.0709
wR = 0.2119
wR = 0.0684
wR = 0.0628
wR = 0.0770
wR = 0.1851
2
2
2
2
2
2
R indices (all data)
R1 = 0.0393;
R1 = 0.0886;
R1 = 0.0416;
R1 = 0.0320;
R1 = 0.0326;
R1 = 0.0702;
wR = 0.0771
wR = 0.2278
wR = 0.0732
wR = 0.0652
wR = 0.0782
wR = 0.1882
2
2
2
2
2
2
1
9

CrystEngComm
Page 20 of 21
3
Largest diff. peak / hole, e/Å 0.360 / −0.216
CCDC no. 1879950
2.204 / −0.929
0.642 / −0.459
0.379 / −0.345
0.473 / −0.595
1.449 / −1.069
1879951
1879952
1879953
1879954
1879955
2
0

Page 21 of 21
CrystEngComm
Certain modifications of the synthetic conditions lead to six novel Zn(II) complexes with
View Article Online
octafluorobiphenyl-4,4'-dicarboxylate, thus enriching the knowledge on the coordination
DOI: 10.1039/C9CE00073A
chemistry of perfluorinated ligands.