CuI-based coordination polymers with 2-thiazolyl sulfide ligands: First examples

Article abstract of DOI:10.1016/j.poly.2018.05.045

The reaction of CuI with 2-(methylthio)thiazole (MTT) in a 1:1 or 2:1 molar ratio (MeCN, rt, 1 h) leads to the coordination polymer [CuI(MTT)]_n (CP1) or [(CuI)₂(MTT)]_n (CP2), respectively. CP1 consists of (–Cu–I–Cu–I–)_n zigzag chains wherein the adjacent Cu atoms are bridged by the MTT ligand through the thiazole N and sulfide S atoms. 1-D chains of CP2 are assembled from corner-sharing [CuI₃N] and [CuI₃S] tetrahedra, which alternate in a zigzag fashion. By contrast, 2-(methylthio)benzothiazole (MTBT) reacts with CuI, regardless of the reactants ratio, to give the dinuclear complex [Cu₂I₂(MTBT)₂], where the planar [Cu(μ₂-I)]₂ core is supported by the two ligands in the N-monodentate manner. At ambient temperature, CP1 exhibits a weak yellow luminescence (λ_max = 570 nm), while CP2 emits in the deep-red region (λ_max = 705 nm).

Full text of DOI:10.1016/j.poly.2018.05.045

Polyhedron 151 (2018) 171–176
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
CuI-based coordination polymers with 2-thiazolyl sulfide ligands: First
examples
Alexander V. Artem’ev a, , Denis G. Samsonenko a,b, Olga V. Antonova a
⇑
a Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Akad. Lavrentiev Ave., Novosibirsk 630090, Russia
b Novosibirsk State University, (National Research University), Department of Natural Sciences, 2, Pirogova Str., Novosibirsk 630090, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of CuI with 2-(methylthio)thiazole (MTT) in a 1:1 or 2:1 molar ratio (MeCN, rt, 1 h) leads to
the coordination polymer [CuI(MTT)]n (CP1) or [(CuI)2(MTT)]n (CP2), respectively. CP1 consists of (–Cu–I–
Cu–I–)n zigzag chains wherein the adjacent Cu atoms are bridged by the MTT ligand through the thiazole
N and sulfide S atoms. 1-D chains of CP2 are assembled from corner-sharing [CuI3N] and [CuI3S] tetrahe-
dra, which alternate in a zigzag fashion. By contrast, 2-(methylthio)benzothiazole (MTBT) reacts with CuI,
Received 1 February 2018
Accepted 15 May 2018
Available online 26 May 2018
Keywords:
Copper(I)
Thiazoles
Sulfide ligands
Luminescence
Coordination polymers
regardless of the reactants ratio, to give the dinuclear complex [Cu2I2(MTBT)2], where the planar [Cu(l2
-
I)]2 core is supported by the two ligands in the N-monodentate manner. At ambient temperature, CP1
exhibits a weak yellow luminescence (kmax = 570 nm), while CP2 emits in the deep-red region (kmax
=
705 nm).
Ó 2018 Elsevier Ltd. All rights reserved.
1. Introduction
which significantly depend on the structure of ligand used and
the crystallization conditions [16–26]. In this context, extension
of the sulfides scope over essentially new ligands can, firstly, pro-
vide access to new original functional CuHal-based CPs and, sec-
ondly, gain an insight into the structure-photophysical properties
relationship of these compounds.
In this work, to test hetaryl sulfide ligands of the type Het–SR
(R = alkyl or aryl; Het = N-heterocyclic group) for the synthesis of
Cu(I) halide CPs, we have carried out the reaction of CuI with 2-
(methylthio)thiazole and its benzene-fused analog. Note, the neu-
tral hetaryl sulfides (Het–SR, where Het = N-heterocyclic unit) with
a 1,3-disposition of the heterocyclic N and sulfide S donor (–SR)
atoms, to our knowledge, have never been used in the coordination
chemistry of copper(I) ions.
Over the past decades, neutral copper(I) halide-based coordina-
tion polymers (CPs) have attracted increasing attention due to
their rich structural diversity and intriguing photophysical proper-
ties [1–4]. The CuxIy inorganic skeletons in these CPs can contain
the most diverse structural motifs, ranging from 1-D zigzag [CuI]n
chains to more complicated 2-D and 3-D networks [2]. However, it
should be noted that the structures of Cu(I) halide CPs are still
hardly predictable despite the great body of published data [2].
In terms of the photophysical properties, many of such CPs exhibit
intense solid state luminescence as well as thermo- [5–7],
mechano- [6,8,9] and vapochromic [10] luminescence associated
with Cuꢀ ꢀ ꢀCu interactions. Moreover, CuI-based CPs were demon-
strated to show non-linear optical properties [11] as well as lumi-
nescent sensing toward O2 [12] and nitrobenzene [13].
Currently, the most studied neutral Cu(I) halide CPs are those
supported by N- or P-donor ligands, while the S-donor ligands
are less explored, although they are very promising for the self-
assembly of CPs. For instance, the application of organic sulfides
as assembling ligands offers exciting possibilities for the construc-
tion of unique 1-D, 2-D and even 3-D CPs containing CuxIy cluster
cores as secondary building units [14,15]. These CPs often feature
fascinating emission characteristics and interesting topologies,
2. Experimental details
2.1. General information
2-(Methylthio)thiazole (98%, TCI), 2-(methylthio)benzothiazole
(97%, Aldrich), CuI (98%, Alfa Aesar) and MeCN (HPLC grade, Cry-
ochrom) were commercial products. FT-IR spectra were measured
on a Bruker Vertex 80 spectrometer. Thermogravimetric analyses
were carried out under He at a 10 °C/minꢁ1 heating rate using a
NETZSCH STA 449 F1 Jupiter STA up to 700 °C in a closed Al2O3
pan. The elemental analyses were performed on a MICRO cube
analyzer.
⇑
Corresponding author.
E-mail address: chemisufarm@yandex.ru (A.V. Artem’ev).
https://doi.org/10.1016/j.poly.2018.05.045
0277-5387/Ó 2018 Elsevier Ltd. All rights reserved.

172
A.V. Artem’ev et al. / Polyhedron 151 (2018) 171–176
XPRD analyses were performed on a Shimadzu XRD-7000
diffractometer (Cu K radiation, Ni – filter, 3–35° 2h range, 0.03°
2h step, 5s per point).
598 (vw), 698 (w), 719 (w), 760 (s), 935 (w), 974 (m), 1013 (w),
a
1045 (m), 1090 (m), 1107 (w), 1124 (w), 1155 (vw), 1250 (w),
1279 (vw), 1314 (w), 1418 (vs), 1452 (m), 1562 (w), 2909 (w),
2980 (w), 3053 (vw).
2.2. X-ray crystallography
Diffraction data for single-crystals of 1–3 were obtained on an
automated Agilent Xcalibur diffractometer equipped with an area
3. Results and discussion
AtlasS2 detector (graphite monochromator, k(Mo K
Å, x-scans) at 130 K. Integration, absorption correction and deter-
a) = 0.71073
3.1. Synthesis
mination of unit cell parameters were performed using the CrysA-
lisPro program package [27]. The structures were solved by the
dual space algorithm (SHELXT [28]) and refined by the full-matrix
least squares technique (SHELXL [28]) in the anisotropic approxima-
tion (except for hydrogen atoms). Positions of the hydrogen atoms
of the organic ligands were calculated geometrically and refined in
the riding model. The crystallographic data and details of the struc-
ture refinements are summarized in Table S1.
After a series of experiments, we have established that treat-
ment of CuI with 2-(methylthio)thiazole (MTT) under mild condi-
tions (rt, acetonitrile, 1 h) affords, depending on the molar ratio
of the reactants, either the [CuI(MTT)]n (CP1) or [(CuI)2(MTT)]n
(CP2) 1-D CPs (Scheme 1). At a CuI/MTT molar ratio of 1:1.1, CP1
with a (ACuAIA)n chain is selectively obtained in 87% yield. When
the CuI/MTT ratio is 2:1, CP2 is formed in almost a quantitative
yield. As seen from Scheme 1, the MTT ligand in both CPs exhibits
the 1,3-N,S bridging mode [l-g g
1(N), 1(S)]. As expected, the thia-
2.3. Photophysical measurements
zole sulfur atoms are not involved in coordination with the copper
ion.
Photoluminescence and excitation luminescence spectra, and
quantum yields were recorded using a Fluorolog-3 (Horiba Jobin
Yvon) at room temperature. Fluorolog-3 was equipped with a
450 W ozone-free Xe lamp, an integration sphere, and double grat-
ing excitation and emission monochromators. The emission and
excitation spectra were corrected for the source intensity (lamp
and grating) and emission spectral response (detector and grating)
by standard correction curves. The luminescence decays
(Figs. S11–13) were measured on the same instrument.
Our attempts to synthesize CPs using 2-(methylthio)benzothia-
zole (MTBT) in the reaction with CuI have led to an iodo-bridging
dinuclear complex [Cu2I2(MTBT)2] (3), containing three-coordi-
nated Cu atoms (Scheme 2). Each MTBT ligand in this complex is
coordinated to the metal atom via the thiazole N atom. Apparently,
the bulkier structure of the MTBT ligand encumbers the self-
assembly of polymeric chains so that the formation of the discrete
complex becomes more preferable. Note, the CuI/MTBT ratio (e.g.
1:1 or 2:1) does not affect the structure of the reaction product.
Under the best conditions (equimolar CuI/MTBT ratio, r.t., acetoni-
trile), the yield of complex 3 reaches 94%.
2.4. Synthesis and characterization data
All the compounds obtained are air-stable colorless powders
and are soluble in acetonitrile. They have been characterized in
the solid state by single crystal X-ray diffraction analysis, FT-IR
(Figs. S4–6) and fluorescent spectroscopy. The thermal stability
has also been determined using thermogravimetric analysis/differ-
ential thermal analysis (TGA/DTA). The phase purity of prepared
samples of 1–3 has been confirmed by powder X-ray diffraction
determination (Figs. S1–3) and CHN analysis data.
2.4.1. {CuI(MTT)}n (1)
To a solution of 2-(methylthio)thiazole (112 mg, 0.85 mmol) in
acetonitrile (3 mL), CuI (147 mg, 0.77 mmol) was added and the
mixture was stirred at ambient temperature for 1 h. The formed
precipitate was centrifuged, washed with a small amount of MeCN
and dried in air. Yield: 216 mg (87%). Colorless powder. Anal. Calc.
for C4H5CuINS2 (321.67): C, 14.94; H, 1.57; N, 4.35. Found: C, 14.8;
H, 1.7; N, 4.4%. FT-IR (KBr, cmꢁ1): 430 (vw), 490 (w), 608 (m), 745
(vs), 770 (w), 872 (w), 968 (s), 978 (m), 1049 (m), 1082 (vs), 1150
(s), 1294 (m), 1373 (s), 1412 (m), 1489 (s), 1578 (w), 1645 (w),
1803 (w), 2735 (vw), 2857 (vw), 2907 (w), 2961 (w), 3069 (s),
3086 (m).
2.4.2. {(CuI)2(MTT)}n (2)
To a solution of 2-(methylthio)thiazole (62 mg, 0.47 mmol) in
acetonitrile (3 mL), CuI (180 mg, 0.94 mmol) was added and the
mixture was stirred at ambient temperature for 1 h. The formed
precipitate was centrifuged, washed with a small amount of MeCN
and dried in air. Yield: 218 mg (90%). Colorless powder. Anal. Calc.
for C4H5Cu2I2NS2 (512.12): C, 9.38; H, 0.98; N, 2.74. Found: C, 9.4;
H, 1.1; N, 2.7%. FT-IR (KBr, cmꢁ1): 384 (vw), 494 (w), 608 (m), 733
(vs), 770 (w), 874 (w), 962 (m), 970 (s), 1049 (m), 1080 (vs), 1150
(m), 1294 (m), 1377 (s), 1412 (m), 1420 (m), 1462 (w), 1497 (m),
1614 (vw), 2911 (w), 2988 (w), 3088 (m), 3105 (m).
2.4.3. {Cu2I2(MTBT)2} (3)
To a solution of 2-(methylthio)benzothiazole (84 mg, 0.46
mmol) in acetonitrile (3 mL), CuI (88 mg, 0.46 mmol) was added
and the mixture was stirred at ambient temperature for 1 h. The
formed precipitate was centrifuged, washed with a small amount
of MeCN and dried in air. Yield: 161 mg (94%). Colorless powder.
Anal. Calc. for C16H14Cu2I2N2S4 (743.46): C, 25.85; H, 1.90; N,
3.77. Found: C, 25.9; H, 2.0; N, 3.7%. FT-IR (KBr, cmꢁ1): 424 (w),
Scheme 1. Synthesis of CP1 and CP2. Conditions: r.t., MeCN, stirring, 1 h.

A.V. Artem’ev et al. / Polyhedron 151 (2018) 171–176
173
an irregular zigzag (ACu1ACu2ACu1ACu2A)n chain [\CuACuACu are
111.59(4) and 71.29(3)°], formed by the Cuꢀ ꢀ ꢀCu short contacts of
2.7629(14) and 2.7901(10) Å. Each I atom binds three Cu atoms
in a
tetrahedral environment (
3-I atoms and S(2) or N(1) atoms, respectively. The polymeric
l3-mode. The Cu(1) and Cu(2) atoms are located in a distorted
s
4 = 0.83 and 0.88 [29]) formed by three
l
structure of CP2 can also be described as alternating [CuI3N] and
[CuI3S] tetrahedra aggregated in a corner-sharing and edge-sharing
manner (Fig. 2c). To our knowledge, a similar structure of a (Cu2I2)n
chain was reported only for the CP [Cu4I4(L)2]n bearing the 1,3,4-
thiadiazole-based ligand [37]. The bond lengths and angles around
the Cu atoms as well as Cuꢀ ꢀ ꢀCu distances in CP2 are comparable
with those in the known CP [16–26].
Scheme 2. Synthesis of 3.
ꢀ
Complex 3 crystallizes in the P1 space group. Its asymmetric
3.2. Crystal structures of 1–3
unit consists of one half of a [Cu2I2(MTBT)2] molecule. Its Cu2I2 core
shows a rhomboid-shaped planar structure (Fig. 3) with the
Cuꢀ ꢀ ꢀCu distance being 2.4981(6) Å, which implies the existence
of a cuprophilic interaction. Each Cu atom of 3 is coordinated by
CP1 crystallizes in the P21/c space group and its asymmetric
motif contains the CuI unit ligated by the 2-methylthiothiazole
molecule via the N atom (Fig. 1a). The Cu atoms of CP1 are linked
by l2-bridging I atoms to form 1-D zigzag (CuI)n chains along the c
axis (Fig. 1b). Each Cu atom is also bonded with N and sulfide S
two
l2-I atoms and the N atom of the ligand, thus adopting a
trigonal planar geometry. Each Cu atom deviates from the mean
0
‘‘N1AI1AI1 ” plane toward the S atom by 0.041 Å. A possible
atoms from two neighboring ligands, adopting a distorted [I2NS]
intramolecular Cu(1)–S(2) interaction is hardly probable since this
distance [3.3062(7) Å] is longer than the sum of van der Waals
radii for these atoms (3.20 Å [38]). The benzothiazole cycle is
nearly perpendicular to the Cu2I2 plane, with a torsion angle of
75.78°. In the crystal packing of 3, there are no specific interactions
between the molecules except for van der Waals ones. On the
whole, the bond lengths and angles in 3 are comparable with those
in similar Cu2I2 complexes [39].
tetrahedral geometry
distance within these chains is too long [3.8369(13) Å] for any
metallophilic interaction. Each MTT ligand simultaneously binds
(
s
4 = 0.94 [29]). The shortest Cuꢀ ꢀ ꢀCu
two
l2-I-bridged Cu atoms forming a 6-membered chelating
‘‘CuAIACuANACAS” ring. The latter adopts a boat conformation
with the torsion angle between the mean N1AC3AS2ACu1 and
S2ACu1AI1ACu1 planes being 54.472(186)°. Both CuA
l2-I bonds
have almost the same length. The CuAIACuAI and IACuAIACu tor-
sion angles in CP1 are 155.645(39) and 110.544(40)°, respectively.
Analysis of CCDC database reveals that the topology of (ACuAIA)n
chain in CP1 is close to that of the 2-D coordination polymer [CuI
(pyrimidine)]n [30] (see Fig. S14). Note that (ACuAIA)n chains with
other topologies are also known [31–36].
3.3. Luminescent properties
The luminescent properties of the synthesized compounds were
studied for solid samples at room temperature. Upon photoexcita-
tion, compounds CP1, CP2 and 3 exhibit a weak emission with
quantum yields of ꢂ1, 1.2 and 2.5%, respectively. Fig. 4 displays
the excitation and emission spectra of the solid powders at 298
K. The emission and excitation maxima, lifetimes and photolumi-
nescence quantum yields at room temperature are summarized
in Table 1. The excitation spectra of CP1, CP2 and 3 show quite nar-
row bands centered at 430, 400 and 360 nm, correspondingly. The
emission spectra appear to be broad and unstructured thus
ꢀ
CP2 crystallizes in the P1 space group and its asymmetric unit
consists of the [Cu2I2(MTT)] fragment, as depicted in Fig. 2a. This
CP contains a double-stranded (Cu2I2)n chain ligated on both sides
by MTT ligands in the 1,3-N,S bridging mode (Fig. 2b). The formed
6-membered chelating ‘‘CuAIACuANACAS” rings have a boat con-
formation with the torsion angle between mean N1AC3AS2ACu1
and S2ACu1AI1ACu1 planes being 55.894(118)°. The Cu atoms form
Fig. 1. (a) The asymmetric unit of CP1; (b) Fragment of its 1-D chain; (c) polyhedral representation of the Cu(I) coordination environments in the 1-D chains of 1. Selected
bond lengths (Å) and angles (°): Cu(1)ACu(10) 3.8369(13), Cu(1)AI(1) 2.6091(10), Cu(1)AI(10) 2.6120(11), Cu(1)AN(1) 2.033(6), Cu(1)AS(20) 2.336(2), Cu(1)AI(1)ACu(10)
94.59(3), I(1)ACu(1)AI(10) 111.36(4), N(1)ACu(1)ACu(1) 107.54(17), N(1)ACu(1)AI(10) 109.46(17).

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A.V. Artem’ev et al. / Polyhedron 151 (2018) 171–176
Fig. 2. (a) The asymmetric unit of CP2; (b) Fragment of its1-D chain showing Cuꢀ ꢀ ꢀCu short contacts; (c) polyhedral representation of the Cu(I) coordination environments in
the 1-D chains of CP2. Selected bond lengths (Å): Cu(1)ACu(10) 2.7629(14), Cu(2)ACu(20) 2.7202(16), Cu(1)ACu(20) 2.7901(10), Cu(1)AI(1) 2.6628(9), Cu(10)AI(1) 2.6792(10),
Cu(20)AI(1) 2.7195(8), Cu(2)AN(1) 2.018(4), Cu(1)AS(2) 2.3533(15), Cu(1)AI(2) 2.6173(8), Cu(2)AI(2) 2.6339(8), Cu(2)AI(20) 2.6704(9).
Fig. 3. Molecular structure of 3. Selected bond lengths (Å) and angles (°): Cu(1)ACu
(10) 2.4981(6), Cu(1)AI(1) 2.5364(3), Cu(1)AI(10) 2.5863(3), Cu(1)AN(1) 1.9651(18),
Cu(1)AS(2) 3.3062(7), I(1)ACu(1)AI(10) 121.636(12), Cu(1)AI(1)ACu(10) 58.364
(11), N(1)ACu(1)ACu(10) 171.99(5), N(1)ACu(1)AI(1) 125.54(5).
indicating a MLCT character of the emissive state, which is typical
for Cu(I) complexes [40]. It ta noteworthy that CP2 emits in the
Fig. 4. Normalized solid state excitation (dashed lines) and emission (solid lines)
deep-red region (700 nm) of the spectrum, which is still an uncom-
mon phenomenon for Cu(I) complexes [41]. Thus, the structure of
the (CuI)x chain in CP1 and CP2 strongly affects the energies of
their emissions and lifetimes. The red-shift of the emission maxi-
mum, observed on going from CP1 to CP2, can be tentatively
explained by the Cuꢀ ꢀ ꢀCu interactions in CP2, which are known
to be responsible for the modulation of emission energies [42].
All the complexes show three-exponential decay dynamics and
lifetimes in the microsecond region (Table 1) that indicates the
spectra of CP1 (kex = 430 nm), CP2 (kex = 400 nm) and 3 (kex = 360 nm) at 298 K.
triplet origin of the emissions. The observation of three lifetimes
is probably due to specific intermolecular interactions in the crys-
tal packing of 1–3. Taking into account the results of recent work
[41], the origin of the luminescence in compounds 1–3 may be
attributed to 3MLCT state.

A.V. Artem’ev et al. / Polyhedron 151 (2018) 171–176
175
Table 1
Luminescence properties of complexes 1–3 in the solid state at 298 K.
Compound
kex (nm)a
kem (nm)a
s
[l
s (An)]b
PLQY (%)c
CP1
455
570
0.008(77)
0.142(5)
<1
1.983(18)
0.057(13)
0.224(57)
1.169(30)
0.008(9)
CP2
3
390
350
700
540
1.2
2.5
0.070(71)
1.593(20)
a
b
c
Emission or excitation maximum.
Emission decays were analyzed with three components I = A1exp(ꢁt/s1) + A2exp(ꢁt/s2) + A3exp(ꢁt/s3).
Photoluminescence quantum yields in the solid state.
a
1,3-N,S bridging mode
[
l-
g
1(N),
g
1(S)]. Meanwhile, 2-
(methylthio)benzothiazole in the reaction with CuI affords a dinu-
clear complex [Cu2I2(MTBT)2], wherein each three-coordinated Cu
atom is bonded with the N atom of the MTBT ligand. All the above
compounds in the solid state at room temperature show a weak
luminescence centered at 570, 705 and 530 nm for [CuI(MTT)]n,
[(CuI)2(MTT)]n and [Cu2I2(MTBT)2], respectively. It is noteworthy
that [(CuI)2(MTT)]n displays a deep-red (700 nm) photolumines-
cence, thus representing a rare example of a Cu(I) complex show-
ing an emission in this region. The results described contribute to
the coordination chemistry of both sulfide ligands and Cu(I) halide
CPs.
Acknowledgement
We thank Federal Agency for Scientific Organizations for
funding.
Appendix A. Supplementary data
Fig. 5. TGA traces for 1–3.
CCDC 1815946–1815948 contains the supplementary crystallo-
graphic data for 1–3. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at https://doi.org/10.
1016/j.poly.2018.05.045.
3.4. Thermal properties
The thermal stability of the above compounds has been
studied by TGA/DTA under a helium atmosphere (for details, see
Figs. S7–9). As seen from Fig. 5, CP2 and complex 3 exhibit similar
single-step decomposition trends, losing the ligand molecules at
120–170 and 120–190 °C, correspondingly. The weight losses for
CP2 and 3 (25.1 and 47.5%, correspondingly) well agree with the
calculated values (25.6 and 48.8%) for CuI. Above ca. 500 °C, the
CuI residue begins to vaporize. By contrast, CP1 demonstrates a
two-step decomposition into CuI at ca. 90–130 and 130–150 °C.
We believe that in the first step, CP1 eliminates one ligand mole-
cule to form CP2, [(CuI)2(MTT)]n, which above 130 °C further
decomposes into CuI. The calculated values of the weight loss for
these stages (23.6 and 17.1%) roughly correspond to the calculated
data (27.4 and 20.9%) for the above processes.
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