Sulfonate-Ligated Coordination Polymers Incorporating Paramagnetic Transition Metals

Article abstract of DOI:10.1002/ejic.201900285

The functionalized linker SNDC (4,8-disulfonyl-2,6-naphthalenedicarboxylate) has been incorporated into 2D extended structures featuring Fe^II or Co^II. These materials are isostructural and exhibit coordination via both the carboxylate and sulfonate groups of the SNDC linker. The variable temperature magnetic behavior of the Fe^II and Co^II materials has also been measured. A simplified model of these systems implies weak (|J| < 5 cm^–1) antiferromagnetic coupling, as is expected for a superexchange mechanism operating through the carboxylate paddlewheels. The combination of functionalized linkers, such as SNDC, with paramagnetic metal centers is a promising pathway towards functionalized materials, and the coordination polymers reported join a small class of known materials featuring SNDC.

Full text of DOI:10.1002/ejic.201900285

A Journal of
Accepted Article
Title: Sulfonate-Ligated Coordination Polymers Incorporating
Paramagnetic Transition Metals
Authors: Airi Kawamura, Alexander S. Filatov, and John Stuart
Anderson
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201900285
Link to VoR: http://dx.doi.org/10.1002/ejic.201900285

10.1002/ejic.201900285
European Journal of Inorganic Chemistry
COMMUNICATION
Sulfonate-Ligated Coordination Polymers Incorporating
Paramagnetic Transition Metals
Airi Kawamura[a], Alexander S. Filatov[a], and John S. Anderson*[a]
Abstract: The functionalized linker SNDC (4,8-disulfonyl-2,6-
naphthalenedicarboxylate) has been incorporated into 2D extended
structures featuring Fe(II) or Co(II). These materials are isostructural
and exhibit coordination via both the carboxylate and sulfonate groups
of the SNDC linker. The variable temperature magnetic behavior of
the Fe(II) and Co(II) materials has also been measured. A simplified
model of these systems implies weak (|J| < 5 cm-1) antiferromagnetic
Scheme 1. Conditions for the solvothermal syntheses of the M2(SNDC)(DMF)5
coupling, as is expected for a superexchange mechanism operating
through the carboxylate paddlewheels. The combination of
functionalized linkers, such as SNDC, with paramagnetic metal
centers is a promising pathway towards functionalized materials, and
the coordination polymers reported join a small class of known
materials featuring SNDC.
materials.
classic linkers. In this way, the desirable properties of the classic
linkers can be combined with attractive substituent properties
such as modulation of electronic properties through the additional
coordinating functionalities.
Sulfonate, as a strongly electron withdrawing group, should
modulate the redox potentials of a conjugated aryl group and
potentially allow redox activity or the installation of radical
character. Some stable organic radicals bearing sulfonate or
sulfuranyl groups have been reported, but frequently show a poor
ability to coordinate to metal sites.3 Coordination polymers
incorporating sulfonate functionalized ligands are fairly rare, and
the bulk of reported structures are Ag containing materials.4,5
There are currently less than a dozen reports of sulfonate
functionalized ligands in coordination polymers containing
transition metals,6 and among these most contain diamagnetic
metal sites. Typically, extended networks of metals and sulfonate-
functionalized ligands have been layered materials and the
primary proposed applications of these compounds have arisen
from structural features – for example, gas or dye absorption
between layers or in pores.
Introduction
The foundational work in the field of extended metal-organic
materials focused primarily on the utilization of commercially
available and largely chemically stable linkers such as aryl
polycarboxylates, pyrazines, and pyridines, which produced many
highly stable and porous materials appropriate for applications
such as gas separation and sorption.1 There has recently been a
drive to incorporate additional properties into extended solids
such as catalytic activity, exotic magnetic and optical behavior,
electrical and ionic conductivity, medicinal functionality and
more.2 However, realization of these properties typically
necessitates the inclusion of other linkers or substituents. Classic
ligands such as carboxylates are favorable components to
incorporate into extended solids as they engender strong metal
binding to create stable crystalline materials, and have the
appropriate size and rigidity to instill porosity. Unfortunately, these
same linkers are also typically insulating and diamagnetic, limiting
interesting magnetic or electronic properties. Conversely, many
ligands with desirable secondary functionalities lack the strong
metal binding necessary for stable and crystalline materials. The
incorporation of new binding motifs into coordination polymers is
therefore both challenging and relatively underexplored. One
strategy to expand this area is the further functionalization of
Of this larger group of potential linkers, the functionalized
dicarboxylate
ligand
SNDC
(4,8-disulfonyl-2,6-
naphthalenedicarboxylate, Scheme 1 left) has been utilized in a
small number of metalated complexes and extended materials,
with preferential binding via sulfonate or carboxylate groups in
addition to the multiple binding modes of both groups resulting in
a large variety of structural motifs. These reported materials have
targeted many of the aforementioned application areas, including
proton conductivity, catalysis, magnetism, and luminescence.6h-k,7
Wanting to further investigate coordination polymers
incorporating this linker, we have synthesized two 2D extended
materials, M2(SNDC)(DMF)5 with M = Fe(II), Co(II). These are the
first reported examples of extended solids containing SNDC and
paramagnetic transition metals and join the single previous
example of mixed valent Fe(II)/Fe(III) molecular triangles reported
by Trikalitis et al,7a as the only reported cases of any paramagnetic
transition metal bound to the SNDC ligand.
[a]
Airi Kawamura, Dr. Alexander S. Filatov, Prof. Dr. John S. Anderson
Department of Chemistry
The University of Chicago
929 E. 57th St,
Chicago, IL, 60637
E-mail: jsanderson@uchicago.edu
Homepage: jsandersonlab.org
Supporting information for this article is given via a link at the end of
the document.
Results and Discussion
Synthesis and Stability
The H4SNDC proligand was prepared according to published
procedures by sulfonation of 2,6-naphthalenedicarboxylic acid
with fuming sulfuric acid.7,8 The M2(SNDC)(DMF)5 (M = Fe(II) or
The crystal structure for Fe2(SNDC)(DMF)5 (CCDC 1902808) can be
accessed free of charge from the Cambridge Crystallographic Data
Centre.
This article is protected by copyright. All rights reserved.

10.1002/ejic.201900285
European Journal of Inorganic Chemistry
COMMUNICATION
Figure 2. The X-ray powder diffraction pattern of M2(SNDC)(DMF)5, M = Fe(II),
Co(II) collected at room temperature and the theoretical diffraction pattern
calculated from the single crystal X-ray diffraction data for Fe2(SNDC)(DMF),
collected at 100 K.
and paddlewheel Fe sites is 2.056 Å, σ = 0.008, and the Fe–O
bond length corresponding to the bound DMF is 2.039(5) Å. At the
other Fe(II) site, the binding via sulfonates yields zig-zag chains
of Fe and SNDC embedded within the 2D plane. The sulfonate O
atoms bound to Fe(II) are cis- to one another, and O atoms from
DMF occupy the remaining four coordination sites. The geometry
of these Fe(II) sites is close to perfectly octahedral with a standard
deviation from 90° of σ = 3.2°. The average Fe–O bond lengths
of these Fe sites are markedly longer (2.13 Å, σ = 0.03 Å) than
those of the paddlewheel Fe sites. The average lengths of the Fe–
O bonds corresponding to the bound SNDC and DMF at this site
are fairly similar at 2.14 Å and 2.12 Å, respectively. The nearest
FeꞏꞏꞏFe separation outside of the paddlewheel unit is 7.287(2) Å
and corresponds to the distance between a carboxylate-bound Fe
and a sulfonate-bound Fe, whereas the FeꞏꞏꞏFe separations
between the paddlewheel units or between sulfonate bound Fe
sites are >10 Å. PLATON analysis indicates that there is minimal
solvent accessible void space (4.5%) in the structure. From the
structure, it can be observed that the Fe-SNDC framework (Figure
1) creates diamond-shaped pores within the layers. However, the
Fe-bound DMF molecules occupy these spaces leading to
negligible overall void space. The predicted lack of porosity is
supported by N2 gas uptake measurements which imply a low
amount of gas adsorption (Figure S1).
Figure 1. The molecular structure of Fe2(SNDC)(DMF)5 (A) perpendicular to
and (B) parallel to the extended 2D plane. The N and C atoms of bound DMF
molecules have been omitted for clarity on the right side of figure A, and in all
but the right unit of figure B. H atoms have been omitted for clarity. Fe is orange,
S is yellow, O is red, N is blue, and C is grey. All atoms are shown in a ball and
stick model.
Co(II)) materials were prepared by solvothermal synthesis using
malonic acid as a templating agent to improve crystallinity
(Scheme 1). The Fe(II) and Co(II) materials are obtained as
orange and purple microcrystalline solids in yields of 71% and
74%, respectively. These materials are stable for over three
months under N2 atmosphere and are stable in dry air, as
evidenced by negligible change to overall crystallinity observed
by X-ray powder diffraction (XRPD). Under atmospheric air,
however, degradation occurs over the course of hours likely due
to atmospheric water, as these materials dissolve in water
(Figures S4 and S5). Differential scanning calorimetry (DSC)
analysis indicates that these materials are thermally stable up to
approximately 250 °C under flow of N2 and do not exhibit any
significant endothermic transitions below these temperatures
(Figures S6 and S7).
Structure
Single crystal X-ray diffraction (SXRD) data acquired on
Although a single crystal structure of Co2(SNDC)(DMF)5 could not
be obtained, XRPD data offer insight on the structure of this
material. Both of the M2(SNDC)(DMF)5 materials exhibit XRPD
patterns consistent with the pattern calculated from the space
group and unit cell parameters determined from the SXRD data
of Fe2(SNDC)(DMF)5 (Figure 2), indicating that these materials
are isostructural and consist of a single crystalline phase.
ꢀ
Fe2(SNDC)(DMF)5 reveals a triclinic P1 space group featuring
Fe(II) centers bound both through the sulfonate and carboxylate
groups of SNDC. The carboxylate bound Fe(II) atoms form a
paddlewheel motif which forms an extended 2D plane. The axial
site of the paddlewheel is capped by DMF, preventing an
extended 3D network from forming via pillaring of the planes. The
FeꞏꞏꞏFe separation in these paddlewheels is 2.869(1) Å which is
typical for Fe(II)/Fe(II) paddlewheel units.9 The Fe–O–C–O–Fe
planes are almost perfectly orthogonal to one another at 88.8(2)°.
The average Fe–O bond length between the carboxylate O atoms
Magnetic Properties
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10.1002/ejic.201900285
European Journal of Inorganic Chemistry
COMMUNICATION
suggests that the exchange from the shortest M–O–C–O–M
pathway is likely dominant over pathways across the aryl portion
of SNDC which span 7+ atoms. The net coupling between the two
paddlewheel Fe sites with spins S1 and S2 (see Figure 4) is
designated as J12 and corresponds to the cumulative exchange
mediated by all four carboxylate bridge pathways between these
spin centers. The next nearest Fe/Fe interaction (see above) is
between a paddlewheel Fe site (S1 or S2) and its nearest
sulfonate-bound Fe neighbor (spin center S3 or S4, respectively),
and a secondary coupling here (J13 = J24) would be expected to
be much smaller than between paddlewheel sites. We can
estimate the effects of these couplings using the following
Hamiltonian:
Ĥ = ꢁ1μBꢂ∙ꢃ1 + ꢁ2μBꢂ∙ꢃ2 + ꢁ3μBꢂ∙ꢃ3 + ꢁ4μBꢂ∙ꢃ4 – ꢄ12ꢃ1ꢃ2 –
ꢄ13ꢃ1ꢃ3 – ꢄ24ꢃ2ꢃ4
where we make the assumption that any other J values or orbital
contributions should be negligible. Here, g is the g-factor, μ is
magnetic moment, β is the Bohr magneton, H is the applied field,
and S is the spin. It should also be noted that the paddlewheel Fe
sites are crystallographically equivalent, and we therefore set the
S and g values of these sites to be equal (e.g. g1 = g2). The same
constraint was placed between the two crystallographically
equivalent sulfonate bound Fe sites, and correspondingly
between the J13 and J24 values.
The Fe(II) material is well fit to the above Hamiltonian and
estimated to have a J12 value on the order of -1.7(2) cm-1, and a
J13/J24 value of -0.436(8) cm-1 with corresponding g values of
2.20(3) and 2.122(2) for sites 1/2 and 3/4, respectively (Figure 3).
The magnetic data for the Co(II) material can also be fit, however
the analysis is less reliable due to significant spin-orbit coupling
leading to a large axial component of the zero-field splitting (ZFS)
parameter, D.13 The obtained fitting parameters must be
interpreted cautiously without an experimentally determined zero-
field splitting value to verify how physically reasonable the fit is.
Nevertheless, we have fit this data with the following Hamiltonian:
Figure 3. Temperature-dependent magnetic susceptibility (χ) data for
M2(SNDC)(DMF)5 with M = Fe(II), Co(II). Black lines are fits to the data as
outlined in the text. The data is normalized to two formula units in order to model
the relevant magnetic pathways.
In the analysis and discussion of the magnetic behaviors of these
materials, we have considered two formula units to capture the
coupling pathways which likely have the most significant
contribution to the overall magnetic properties (see below).
Variable temperature dc molar magnetic susceptibility (χ) was
collected for both of the M2(SNDC)(DMF)5 variants with M = Fe(II)
and Co(II). The Fe(II) material has a room temperature χT of 14.0
cm3K/mol for two formula units (Figure 3). The spin-only χT value
of four non-interacting S = 2 ions in two formula units is 12.0
cm3K/mol, which is in good agreement with the experimental
values when accounting for spin-orbit effects in 6-coordinate high-
spin Fe(II) ions.10 The χT of Fe2(SNDC)(DMF)5 is fairly constant
above 50 K, indicative of an uncoupled system or very weak
coupling. Lippard and coworkers found that one Fe(II)/Fe(II)
carboxylate paddlewheel complex exhibited a small increase in
magnetic moment at low temperatures, presumably due to
ferromagnetic exchange between the Fe(II) centers.9a The lack of
significant coupling in the present case may be due to the 0.1 Å
larger FeꞏꞏꞏFe separation in our system. This hypothesis is
consistent with the observation that other related Fe(II)/Fe(II)
paddlewheel carboxylate complexes with similarly larger FeꞏꞏꞏFe
separations do not exhibit low temperature increases in their χT
values.9a
The Co(II) material has a room temperature χT of 12.0 cm3K/mol
for two formula units. Although the spin-only χT value of four non-
interacting S = 3/2 ions in two formula units is 7.50 cm3K/mol, a
significantly elevated χT observed for Co(II) ions is a well-
documented phenomenon arising from unquenched spin-orbit
coupling.11 Upon cooling below 300 K, χT decreases continuously.
Concretely assigning the origin of this decrease is difficult due to
convolutions between antiferromagnetic interactions and spin-
orbit coupling effects.
Figure 4. Designation of spin centers and the magnetic exchange interactions
that are most likely to contribute to the bulk magnetic properties of the
M2(SNDC)(DMF)5
materials.
From
the
molecular
structure
of
Fe2(SNDC)(DMF)5: Fe is orange, S is yellow, O is red, and C is grey. Note that
sites designated as S1 and S2 are crystallographically equivalent, as are sites S3
and S4.
Superexchange coupling can be strong over small one- to three-
atom bridges, but is typically weak over longer paths.12 This trend
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10.1002/ejic.201900285
European Journal of Inorganic Chemistry
COMMUNICATION
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Ĥ = ꢁ1μBꢂ∙ꢃ1 + ꢁ2μBꢂ∙ꢃ2 + ꢁ3μBꢂ∙ꢃ3 + ꢁ4μBꢂ∙ꢃ4 – ꢄ12ꢃ1ꢃ2 –
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ꢄ13ꢃ1ꢃ3 – ꢄ24ꢃ2ꢃ4 + ꢅ1[ꢃ1 −ꢃ1(ꢃ1+1)]/3 + ꢅ2[ꢃ2 −ꢃ2(ꢃ2+1)]/3 +
2
2
ꢅ3[ꢃ3 −ꢃ3(ꢃ3+1)]/3 + ꢅ4[ꢃ4 −ꢃ4(ꢃ4+1)]/3
where the additional axial ZFS terms in the Hamiltonian are of the
form ꢅi[ꢃi2−ꢃi(ꢃi+1)]/3. The best fit using this model gives J12 and
J13/J24 values of -4(2) cm-1 and -0.3(2) cm-1, respectively (Figure
3). This fitting also includes g1/2 = 2.6(3) and g3/4 = 2.6(2). We
reiterate that the fit may have significant error due to uncertainty
in the true value of D. In the case of both the Fe(II) and Co(II)
systems the J12 values are in good agreement with previous
reports of magnetic exchange via carboxylates in a syn-syn
binding mode and suggest weak antiferromagnetic exchange in
these materials.14
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Conclusions
Coordination polymers of the type M2(SNDC)(DMF)5 with M =
Fe(II), Co(II) were synthesized and magnetically and structurally
characterized. These materials feature two distinct metal binding
sites – via the sulfonates and carboxylates of the SNDC linker –
to form 2D infinite layers. Both materials exhibit weak
antiferromagnetic coupling, as evidenced by their temperature-
dependent magnetic susceptibilities. These compounds are the
first reported to incorporate the SNDC ligand and paramagnetic
transition metal centers in an extended solid.
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Acknowledgments
This work was supported by the Chicago MRSEC, which is funded
by NSF through Grant DMR-1420709. The University of Chicago
is thanked for startup funds. We thank Professor Nicholas Chilton
for assistance with the PHI software. We thank Andrew McNeece
for assistance with single crystal X-ray diffraction. We thank
Kelsey Collins, Majed Fataftah, and Prof. Danna Freedman for
use of their MPMS. We thank Erik Reinhart and Prof. Richard F.
Jordan for use of their DSC.
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Keywords: magnetic properties • metal organic frameworks •
transition metals • materials science
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10.1002/ejic.201900285
European Journal of Inorganic Chemistry
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Mao, Inorg. Chem., 2006; Zhang, Dalton Trans.,
Colacio, Dalton Trans., 2012, 41, pp 14265-14273.CPs with TM and any sulfonate ligand:
2015; Li, J. Solid State Chem., 2016; Van Der Voort, Dalton Trans., 2017; Tu, J. Mater. Chem. A, 2018; Ng, Inorg. Chem., 2002; Mezei, CrystEngComm, 2012; Xue, Z. Anorg. Allg. Chem., 2015; Kitagawa, Chem. Commun., 2014; Yao, Z. Anorg. Allg. Chem, 2014
NOTE 2: CPs with SNDC: J.Tang
IC 2012; Zhang Dalton Trans 2015; Li J Solid State Chem 2016; Voort Dalton Trans 2017; Tu J Mater Chem 2018
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10.1002/ejic.201900285
European Journal of Inorganic Chemistry
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Magnetism, coordination polymers*
Airi Kawamura[a], Alexander S. Filatov[a],
and John S. Anderson*[a]
Page No. – Page No.
A pair of new coordination polymers featuring sulfonate bound linkers has been
synthesized and characterized by XRD and magnetic measurements. These
represent unusual examples of sulfonate bound to paramagnetic metals in a
coordination polymer.
Sulfonate Ligated Coordination
Polymers Incorporating Paramagnetic
Transition Metals
*one or two words that highlight the emphasis of the paper or the field of the study
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