Solvent Influence in Obtaining Diverse Coordination Symmetries of Dy(III) Metal Centers in Coordination Polymers: Synthesis, Characterization, and Luminescent Properties

Article abstract of DOI:10.1021/acs.cgd.9b01599

Six new Dy(III)-containing coordination polymers (CPs) have been synthesized emphasizing the role of solvent molecules in directing the formation of the Dy(III) coordination sphere which in turn influences the dimensionality of the coordination polymer, t

Full text of DOI:10.1021/acs.cgd.9b01599

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Article
Solvent Influence in Obtaining Diverse Coordination
Symmetries of Dy(III) Metal Centers in Coordination Polymers:
Synthesis, Characterization and Luminescent Properties
Nithi Phukan, SOUMYABRATA GOSWAMI, Sophia Lipstman, Israel Goldberg, and Bharat Kumar Tripuramallu
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b01599 • Publication Date (Web): 25 Mar 2020
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Solvent Influence in Obtaining Diverse Coordination Symmetries of
Dy(III) Metal Centers in Coordination Polymers: Synthesis,
Characterization and Luminescent Properties
Nithi Phukan,*a Soumyabrata Goswami,b Sophie Lipstman,a Israel Goldberg,a and
Bharat Kumar Tripuramallu*c
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aSchool of Chemistry, Sackler Faculty of Exact Sciences, Tel-Aviv University, Ramat-Aviv, 69978
Tel-Aviv, Israel
bDepartment of Chemistry, Amity Institute of Applied Sciences (AIAS), Amity University Kolkata,
Major Arterial Road, Action Area II, Rajarhat, Newtown, Kolkata 700156, India
cChemistry Division, Department of Sciences and Humanities, Vignan Foundation for Science
Technology and Research, Vadlamudi, Guntur 522213, Andhra Pradesh, India
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Abstract:
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Six new Dy(III) containing coordination polymers (CPs) have been synthesized emphasizing the
role of solvent molecules in directing the formation of Dy(III) coordination sphere which in turn
influences the dimensionality of the coordination polymer, thermal stability and emission
properties. Isophthalate based flexible ligand 5-[(anthracen-9-ylmethyl)-amino]-isophthalic acid
(H2L) with different solvents such as DMF (Dimethylformamide), DMA(Dimethylacetamide),
DMSO (Dimethyl sulfoxide), DEF(Diethylformamide) and N-donor linkers phen (1,10-
phenanothroline) and py (Pyridine) was employed to obtain six different coordination polymers
viz.[Dy2(L)2(HCOO)3(DMF).Me2NH2·H2O]n (1), [Dy4 (L)6 (DMA)2(H2O)4·4DMA·4H2O]n
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(2),
[Dy2(L)3(DMSO)3(H2O)2·2DMSO·2H2O]n(3),
[{Dy(L)(DEF)}2(μ2-OH)]n(4),
[Dy2(L)3(phen)2·DMA·7H2O]n (5) and [Dy(L)(NO3)(py)2‧py]n (6) respectively. All the
compounds are characterized by IR spectroscopy, thermogravimetric (TG) analysis, and
unambiguously characterized by single crystal X-ray crystallography. The bulky anthracenyl
group of the linker H2L in combination with the solvent molecules significantly alters the
coordination symmetry of the Dy(III) coordination sphere in the polymers in the manner: D2d in
1, C2v and D4d in 2, C4v and Cs in 3, C5v in 4, D4d in 5 and D2d in 6. The coordination symmetry
plays an interesting role in sensitization of lanthanide emission. The emission maxima of
compounds 1-6 varies from blue region to yellow region significantly due to coordination
symmetry expressed by the Dy(III) centers which in turn depends upon the coordinated solvent
molecule. The thermogravimetric profile indicates the thermal stability of the solvent free
compounds up to 300 °C.
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Introduction:
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The recent achievements in lanthanide coordination polymers (LnCPs) have been quite
impressive due to development of intriguing aesthetic structures as well as their interesting
photophysical properties.1-6 Due to numerous advantages exhibited by lanthanide organic
frameworks in terms of long luminescence lifetimes, substantial stoke shifts and high
photoluminescence efficiencies these materials have received increasing attention.7-9 Both the
components of the framework, i.e. metal centers and organic linkers stimulate the emission
profiles due to ligand-metal charge transfer (LMCT) and metal-ligand charge transfer (MLCT)
transitions.10-12 Fernández et al reported linker sensitized lanthanide centered luminescence of
1D coordination polymers which highlights the role linker selection to manifest the intended
properties.13 The lattice solvent guest molecules in the framework also perform the role of
antenna in transferring the energy to lanthanide centers to exhibit luminescent behavior.14 On the
other hand in the hetero-lanthanide coordination polymer reported by Nogueira and coworkers,
Tb(III) centers sensitize Eu(III) centers leading to enhanced emission of Eu(III) centers.15 Hence
all the components of the framework either linker, guest molecule or metal center significantly
influence the emission behavior of the framework.
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The rational design of LnCPs is quite complicated owing to the higher coordination
numbers and flexible coordination spheres exhibited by the lanthanide metal centers.16-18 Flexible
linkers offer various conformations to meet the coordination requirements imposed by lanthanide
coordination spheres.19-20 The final coordination architectures based on flexible linkers are
cooperatively influenced by the conformation of the linker as well as the coordination sphere of
the metal center.21-22 Hence the utilization of flexible linkers has proven to be one of the
successful strategy to explore the structural diversity of LnCPs.23 In addition, solvent also plays a
vital role in the self- assembly process of coordination polymers directly by coordinating with
metal center or indirectly templating the crystal growth process.24-25 When solvents are directly
involved in the coordination assembly by coordinating with the metal centers depending upon
the bulkiness and steric hindrance of the solvent it influences the symmetry of the metal
coordination sphere thereby affecting self-assembly process.26-27
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In order to gain more insights in the self-assembly process involving the combination of
solvents and flexible linkers to obtain structural diverse lanthanide coordination polymers we
have chosen the 5-[(anthracen-9-ylmethyl)-amino]-isophthalic acid (H2L) as coordinating linker.
Three different functionalities exist in the skeleton of the linker H2L, in which (-CH2-NH-) group
imparts flexibility, position of carboxylate group provides isophthalate connectivity and anthryl
ring increases the bulkiness of the linker as well as influences the emission behavior (Scheme 1).
Earlier the crystal structure dynamics in H2L-Gd(III) coordination polymer during the SCSC
transformation involving the carboxylate shift induced by solvent was studied by Bharadwaj and
co-authors.28 The size dependent mechano-responsive nature of the coordination polymer
constructed by Cd(II) and H2L was reported by Guo et al.29 The coordination architectures
constructed by employing Dy(III) metal centers exemplified the role of tuning coordination
symmetry towards the magnetic interactions30 as well as emission behaviors. 31
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HOOC
COOH
Isopthalate
connectivity
HN
Flexibilty
CH2
Bulkier substituent
&
Chromophore
5-[(anthracen-9-ylmethyl)-amino]-isophthalic acid (H2L)
Scheme 1. Scheme displaying the different functionalities present in the linker H2L.
The unique multifunctional behavior presented in the linker prompts us to study its
coordination self-assembly with different solvents. The linker was employed for complexation
with Dy(III) metal center under different solvents (DMF, DMA, DMSO and DEF), and N-donor
linkers
[Dy2(L)2(HCOO)3(DMF).Me2NH2·H2O]n (1), [Dy4 (L)6 (DMA)2(H2O)4·4DMA·4H2O]n (2),
[Dy2(L)3(DMSO)3(H2O)2·2DMSO·2H2O]n (3), [{Dy(L)(DEF)}2(μ2-OH)]n (4),
phen
and
py
to
obtain
the
reported
compounds
namely:
[Dy2(L)3(phen)2·DMA·7H2O]n (5) and [Dy(L)(NO3)(py)2·py]n (6) respectively. All the
compounds are synthesized under solvothermal conditions and structurally characterized by
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single crystal X-ray diffraction study. Additionally, phase purities of compounds are checked by
Powder X-ray diffraction and thermal studies of the compounds are studied by
thermogravimetric analyses. The luminescent properties of the compounds in the solid state are
also investigated at room temperature.
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Experimental Section:
(a) Materials and methods. All chemicals were obtained from commercial sources and used
without further purification. IR spectra were recorded on a Bruker Tensor 27 system
1
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spectrophotometer in ATR mode. H NMR (400 MHz) and C NMR (100 MHz) spectra were
recorded on Bruker AVANCE-400 spectrometers, in DMSO-d6 with residual DMSO-d5 (1H,
2.50 ppm) or DMSO-d6 (13C, 39.52 ppm) as an internal standard. Solid state emission spectra
were measured on Horiba Jubin Yvan FL3-11 spectrofluorometer at room temperature. Powder
X-ray diffraction (PXRD) measurements were performed on a Rigaku SmartLab diffractometer
at 60 kV, 30 mA, and CuKα radiation (λ = 1.5406 Å), with a scan speed of 1°/min and a step size
of 0.02°. Thermogravimetric analysis (TGA) was carried out on a TA Q500 instrument, using
dry nitrogen atmosphere, at a rate of 20 mL/min.
Synthesis
Synthesis of 5-[(Anthracen-9-ylmethyl)-amino]-isophthalic Acid (H2L).
9- Anthracene carboxaldehyde (1.031 g, 5 mmol) was slowly added to a stirred solution of 5-
aminoisophthalic acid (0.905 g, 5 mmol) in 50 mL of dry methanol and refluxed for 30 minutes.
After cooling the reaction mixture, NaBH4 was slowly added to the reaction mixture at 4ᵒ C. The
solvent was then removed under vacuum and the residue was dissolved in 50 mL of water. The
pH of the reaction mixture was adjusted to 5 by adding acetic acid. The product came out as a
pale-yellow colored precipitate which is collected, washed thoroughly with water and air dried
1
after filtration. Yield: 1.527g (77%). H-NMR: (DMSO-d6, 400 MHz, δ): 11.49 (s, 1H), 8.65 (s,
1H), 8.30 (d, 8Hz, 2H), 8.14 (d, 4Hz, 2H), 7.79 (s, 1H), 7.61 (m, 2H), 7.56 (m, 4H), 6.51 (s, 1H),
5.14 (s, 2H). 13C-NMR: (DMSO-d6, 100 MHz, δ): 167.7, 149.4, 132.4, 131.1, 130.2, 129.5,
129.4, 126.4, 125.8, 125.2, 117.8, 116.3, 103.3, 55.8; ESI-MS: m/z [M−1]: 370.2734 (100%). IR
(cm−1): 3398(s), 2877 (m), 1686 (s), 1600 (s), 1503 (s), 1436 (s), 1272 (s), 949 (m), 893 (m), 728
(s).
[Dy2(L)2(HCOO)3(DMF).Me2NH2·H2O]n (1). A solid mixture of ligand H2L (20.1 mg, 0.05
mmol) and Dy(NO3)3.5H2O (40.1 mg, 0.1 mmol) were taken together in a mixture of 10.0 mL
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DMF/water (2:1 V/V) and stirred for half an hour. The contents were transferred into a Teflon-
lined steel autoclave and heated at 120°C for 48 hours under autogenous pressure then allowed to
cool to room temperature at the rate of 1 °C/min. Colorless crystals of compound 1 were
collected, washed with water and air-dried. Yield 60% based on Dy. Anal. Calcd for
C54H50Dy2N4O16 (1335.92): C, 48.54%; H, 3.77%; N, 4.19%. Found: C, 48.02%; H, 3.12%; N,
3.99%. FT-IR (cm-1): 3375 (w), 3057 (w), 1565 (s), 1382 (s), 777 (s), 729 (s), 408 (s).
[Dy4 (L)6 (DMA)2(H2O)4·4DMA·4H2O]n (2). Dy(NO3)3.5H2O (40.1 mg, 0.1 mmol), ligand H2L
(20.5 mg, 0.05 mmol) and 10.0 mL of DMA/water (1:1 V/V) were added into a 15 mL vial and
sealed. The mixture was then heated at 100 °C for 48 hours under autogenous pressure and
allowed to cool to the room temperature at the rate of 1 °C/min. Yellow crystals of compound 2
were collected, washed with water and air-dried. Yield 60% based on Dy. Anal. Calcd for
C162H160Dy4N12O38 (3532.86): C, 55.07%; H, 4.56%; N, 4.76%. Found: C, 54.22%; H, 4.02%; N,
4.20%. FT-IR (cm-1): FT-IR (cm-1): 3371 (w), 2918 (m), 1541 (s), 1380 (s), 1012 (s), 727 (s),
732 (s), 406 (s).
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[Dy2(L)3(DMSO)3(H2O)2·2DMSO·2H2O]n (3). Dy(NO3)3.5H2O (40.2 mg, 0.1 mmol), ligand
(28.5 mg, 0.08 mmol) were taken together in 10.0 ml DMSO/water (2:1 V/V) and stirred for an
hour. The mixture was transferred into a Teflon lined autoclave and heated to 100°C for 48 hours
under autogenous pressure. Upon cooling to room temperature, yellow crystals of compound 3
were collected in 68 % yield based on Dy. Anal. Calcd for C79H83Dy2N3O21S5 (1895.71): C,
50.05%; H, 4.41%; N, 2.22%; S, 8.46%. Found: C, 49.40%; H, 4.10%; N, 2.01%; S, 8.11%.
FT-IR (cm-1): 3363 (w), 2918 (m), 1541 (s), 1380 (s), 1012 (s), 727 (s), 732 (s), 408 (s).
[{Dy(L)(DEF)}2(μ2-OH)]n (4). Dy(NO3)3.5H2O (40.5 mg, 0.1 mmol), ligand H2L (16.1 mg, 0.04
mmol) and 2.0 mL of DEF/water (2:1 V/V) were sealed together in a Teflon lined autoclave and
heated to 120ᵒ C for 48 hours. The reaction vessel was cooled to room temperature at the rate of
1 °C/min to obtain yellow colored crystals of 4, which were collected, dried and washed with
water. Yield 70% based on Dy. Anal. Calcd for C56H52Dy2N4O13 (1313.96): C, 51.18%; H,
3.99%; N, 4.26%. Found: C, 50.98%; H, 3.88%; N, 4.22%. FT-IR (cm-1): 3745 (m), 2923 (m),
1571 (m), 1448 (s), 1386 (s), 1064 (w), 786 (m), 416 (m).
[Dy2(L)3(phen)2·DMA·7H2O]n (5). To the reaction mixture Dy(NO3)3.5H2O (40.8 mg, 0.1
mmol), ligand H2L (27.7 mg, 0.08 mmol) in 10 mL of DMA/water (2:1 V/V), 1,10-
phenanthroline (11.4 mg, 0.06 mmol) was added and sealed in a 15 mL vial. The mixture was
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heated to 100° C for 48 hours under autogenous pressure and then allowed to cool to room
temperature. Yellow crystals of compound 5 were collected from the mixture, washed with water
and air dried to obtain 70 % yield based on Dy. Anal. Calcd for C103H81Dy2N7O15 (1981.66): C,
62.42%; H, 4.12%; N, 4.95%. Found: C, 62.02%; H, 3.95%; N, 4.75%. FT-IR (cm-1): 3305 (w),
1589 (s), 1539 (s), 1386 (s), 1137 (s), 1012 (m), 773 (s), 725 (s), 410 (s).
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[Dy(L)(NO3)(py)2‧py]n (6). Dy(NO3)3.5H2O (40.8 mg, 0.1 mmol), ligand H2L (18.1 mg, 0.05
mmol) and 2 mL of DMF/pyridine (2:1 V/V) were sealed together in a Teflon lined autoclave
and heated to 100° C for 48 hours. The reaction vessel was cooled to room temperature which
results in the formation of red colored crystals of compound 6. Yield 70% based on Dy. Anal.
Calcd for C39H30DyN5O7 (843.14): C, 55.55%; H, 3.59%; N, 8.31%. Found: C, 55.12%; H,
3.19%; N, 8.09%. FT-IR (cm-1): 2914 (w), 1537 (s), 1380 (s), 1091 (m), 838 (w), 730 (s), 412
(s).
Single crystal X-ray diffraction
Single crystal X-ray diffraction measurements performed on Bruker-Apex Duo diffractometer
with IμS microfocus using MoKα radiation. Measurements were carried out at 110 (2) K on
crystals coated with a thin layer of amorphous oil. The structures were solved by direct and
Fourier methods and refined by full-matrix least-squares, using standard crystallographic
software: SHELXT-2014, SHELXL- 2014.32,33 The integrity of the crystalline products 1-6 was
confirmed in each case by repeated measurements of the unit-cell dimensions from different
single crystallites, as well as by matching between the simulated and experimental powder X-ray
diffraction patterns. Compounds 1, 3, 4 and 5 were found to contain severely disordered
crystallization solvent within the intra lattice voids, which could not be modeled by discrete
atoms. Correspondingly, the contribution of the disordered solvent moieties was subtracted from
the diffraction pattern by the Squeeze procedure and PLATON software. Attempts to locate the
hydrogen atoms for the solvent water molecules in the crystal structure of compounds 1, 2, 3 and
4 through Fourier electron density was failed. However, no attempts were made to fix these
atoms on their parents. Crystal data and structural refinement details for compounds 1−6 are
presented in Table 1. The asymmetric units depicting the solvent molecules of all the compounds
are shown in section S2 of ESI. The geometry around the Dy(III) centers in the compounds 1-6
has been checked using the SHAPE 2.1 program34 and the detailed geometric analyses are
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described in Section S7 (ESI). The TOPOS software package35 was used to analyze the
topological features of the coordination polymers.
Table 1. Crystal data and structural refinement parameters for compounds 1-6.
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Parameters
Empirical formula
Formula weight
Crystal system
Space group
a, Å
Compound 1
C54 H46 Dy2 N4 O15
1315.95
Compound 2
C146H107Dy4 N8 O30
3103.39
Compound 3
C75 H60 Dy2 N3 O17 S3
1696.44
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triclinic
triclinic
triclinic
P-1
9.3064(2)
16.7784(4)
P-1
19.0588(6)
20.0702(6)
P-1
16.3679(10)
16.6434(10)
b, Å
c, Å
17.6166(3)
105.8120(10)
99.9120(10)
97.0510(10)
2565.07(9)
2
1.704
2.964
1300
10313
21.5651(6)
90.4290(10)
93.2740(10)
114.1640(10)
7509.6(4)
2
1.372
2.037
3086
37502
16.8980(10)
71.674(2)
64.728(2)
77.045(2)
3929.9(4)
2
1.434
2.031
1694
19650
α (deg)
β (deg)
γ (deg)
V, Å
Z
ρcalc g/cm3
µ, mm-1
F(000)
Refl collected
Independent refl
GOF
final R indices
[ I˃2σ(I)]
7999
1.025
31028
1.032
16161
1.052
R1= 0.0457
wR2= 0.1049
R1= 0.0637
wR2= 0.1144
99.7
R1= 0.0356
wR2= 0.0850
R1= 0.0458
wR2= 0.0899
99.7
R1= 0.0499
wR2= 0.1321
R1= 0.0621
wR2= 0.1426
98.8
R indices (all data)
Completeness (%)
Parameters
Compound 4
Compound 5
Compound 6
Empirical formula
Formula weight
Crystal system
Space group
a, Å
C56 H52 Dy2 N4 O13
1282.01
C93 H58 Dy2 N7 O12
1790.46
C33.48 H30 Dy N5 O7
836.93
orthorhombic
P b c n
monoclinic
C 2/c
triclinic
P-1
9.8669(4)
10.9295(6)
31.6926(5)
10.6021(2)
28.6493(6)
16.0772(4)
b, Å
c, Å
15.9979(3)
90
90
90
5375.42(17)
4
1.624
2.826
2608
6751
5453
1.056
R1= 0.0511
wR2= 0.1258
R1= 0.0644
wR2= 0.1360
99.8
18.6241(4)
90
91.5870(10)
90
8575.0(3)
4
1.387
1.793
3572
7734
7139
1.063
R1= 0.0244
wR2= 0.0553
R1= 0.0274
wR2= 0.0582
99.4
16.8503(9)
71.989(2)
80.770(2)
67.292(2)
1592.40(14)
2
1.745
2.410
836
5692
α (deg)
β (deg)
γ (deg)
V, Å
Z
ρcalc g/cm3
µ, mm-1
F(000)
Refl collected
Independent refl
GOF
final R indices
[ I˃2σ(I)]
4723
1.066
R1= 0.0503
wR2= 0.1216
R1= 0.0662
wR2= 0.1312
99.6
R indices (all data)
Completeness (%)
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Result and Discussions:
Synthesis
The linker H2L was synthesized by slightly modifying the reported procedure in the literature.28
The synthesis of all the compounds (1-6) were performed under solvothermal conditions by
employing different solvent-water combinations. The reaction temperatures were optimized to
100-120 °C through set of reactions. The infrared spectra of the compounds are consistent with
their single crystal structures (Section S3 ESI). The asymmetric stretching frequencies of the
coordinated carboxylate groups appeared in the region 1380 cm-1. The bands aroused due to
solvent molecules are observed in the region around 3300 cm-1. The synthetic methodology
applied to obtain compounds reported are displayed in scheme 2.
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1000C
1200C
Complex 5
Complex 6
HOOC
COOH
Complex 1
Complex 2
DMA, Phen
DMF
Dy(III)
+
HN
1000C
1000C
DMA
DMF, Py
DMSO
1000C
DEF
1200C
Complex 3
Complex 4
Scheme 2. Scheme representing the synthetic parameters employed for synthesis of compounds
1-6.
Structural description
[Dy2(L)2(HCOO)3(DMF).Me2NH2·H2O]n (1). The colorless block shaped crystals of compound
1 crystallizes in triclinic space group P-1. At high temperature the DMF molecules in the
reaction mixture hydrolyzed to form formic acid and dimethyl ammonium cations which
crystallizes within the lattice acting as counter cation. The asymmetric unit consists of two
crystallographically independent Dy (III) atoms, two deprotonated L2- ligands, three coordinated
formate ions, one coordinated DMF molecule and one dimethyl ammonium cation. Two ligands
L2- present in the asymmetric unit are slightly different from each other in terms of
conformational flexibility provided by the (-CH2-NH-) connectivity in the ligand. The
carboxylate groups of the linkers are completely deprotonated and coordinates to the Dy(III)
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metal centers in μ2-κ4, η2:η2 and μ3-κ4,η2 η1:η1 coordination modes to form a Dy2 dimer. The
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isophthalate coordination mode present in the linker leads to the formation of 1D chain with Dy2-
dimer as building unit (Figure 1a). Both the Dy atoms (Dy1 and Dy2) present in the dimer are
constituted by octa coordinated ‘triangular dodecahedron’ sphere with D2d symmetry as shown in
the Figure 1b (obtained from SHAPE 2.1 program and the detailed geometric analyses are
described in section S7, ESI). The octa coordination sphere around Dy1 is formed by three
oxygen atoms from two different L2- ligands, four oxygen atoms from three coordinated formate
ions and one oxygen atom from coordinated DMF molecule. The other Dy2 coordination sphere
is furnished by five oxygen atoms from three different L2- ligands and three oxygen atoms from
three different formate ions. The Dy-O bond distances 2.296 (5)-2.447 (5) Å falls within normal
range of bond lengths reported for other coordination polymers of dysprosium.36
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Figure 1. (a) Coordination environment around the Dy2 dimer (The skeleton of the linker is
represented by “L” (b) Triangular dodecahedron coordination sphere (D2d) around the Dy(III)
metal centers in compound 1 (c) Representation of one dimensional chain running along the bc
plane (d) 2D sheet like structure and its topological representation (anthracenyl rings are omitted
for clarity).
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Overall the SBU Dy2 dimer in the 1D chain is constructed by four carboxylate groups from four
different L2- ligands, four formate anions in which two are involved in connecting the intra dimer
Dy(III) centers through μ2-κ3,η2 η1 and μ2-κ2,η1 η1 coordination modes and other two in
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connecting the inter dimer Dy(III) centers by μ2-κ2, η1 η1 coordination mode as shown in Figure
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1c. Hence both the formate ion inter dimer connectivity and isophthalate connectivity extend
dimer into two-dimensional network (Figure 1d). The topological expression of the framework is
given by reducing the dimer to node which gives a 4-connected uninodal network and belongs to
sql network with Schläfli symbol {44.62}. The bulky anthracenyl groups are hanged above and
below the plane through the double ordered flexible group (-CH2-NH-). Due to this flexibility the
anthracenyl groups are not perfectly stacked over each other.
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[Dy4 (L)6 (DMA)2(H2O)4·4DMA·4H2O]n (2). Single crystal analysis reveals that compound 2
crystallizes in triclinic space group P-1 and features a 2D coordination polymer. The asymmetric
unit in compound 2 is very large which contains four Dy (III) atoms, six deprotonated L2-
ligands, two coordinated DMA molecules and four coordinated water molecules. The
asymmetric unit contains two different Dy-dimers, in which each dimer is comprised of two
crystallographically independent Dy(III) atoms. The Dy(III) atoms namely Dy1 and Dy2 in one
dimer (represented by A) are presented in eight coordinated ‘biaugmented trigonal prism’ with
C2v symmetry (checked using the SHAPE 2.1 program and the detailed analysis is described in
section S7, ESI), in which the Dy1 coordination sphere is constituted by five oxygen atoms from
four different L2- ligands and one oxygen atom from DMA and two oxygen atoms from two
water molecules, whereas eight oxygen atoms from five different L2- ligands constitute the Dy2
coordination sphere (Figure 2a). In the other Dy-dimer B, the Dy3 present in ‘square antiprism’
(D4d symmetry) coordination geometry constituted by five oxygen atoms from four different L2-
ligands, one oxygen atom from DMA molecule, two oxygen atoms from water molecules and the
Dy4 metal center is furnished by eight oxygen atoms from four L2- ligands in ‘Johnson -
biaugmented trigonal prism’ with C2v symmetry as shown in the Figure 2b. Overall the dimer A
is constituted by six ligands in which four connects the adjacent dimer B on either sides to form
1D chain and other two extends these chains to 2D sheets by connecting the dimer B on adjacent
chains (Figure 2c). Six ligands present in the asymmetric unit are completely deprotonated and
coordinates to Dy(III) metal centers in μ3-κ4,η2 η1:η1 and μ3-κ5,η2 η2:η1 coordination modes. The
:
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anthracenyl rings are freely hanged above and below the plane and twisted from the isophthalate
ring with different torsional angle ranging from 125 to 180°. The 2D coordination network
features 4-c uninodal network with sql topology of point symbol {44.62}.
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Figure 2. (a) Representation of coordination spheres around the Dy(III) metal centers (Dy1 and
Dy2 has same environment and represented as Dy) (b) The coordination environments around
the Dy1Dy2 and Dy3Dy4 dimers (c) 2D coordination layer formed due to isophthalate
coordination connectivity (Coordinated solvent molecules and anthracenyl groups are omitted for
clarity).
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[Dy2(L)3(DMSO)3(H2O)2·2DMSO·2H2O]n (3). By using the solvent DMSO the block-shaped
yellow crystals of 3 were crystallized in triclinic space group P-1 (Table 1). The asymmetric unit
consists of two Dy (III) atoms, three deprotonated L2- ligands, three coordinated DMSO
molecule and two coordinated water molecules. The two metal centers Dy1 and Dy2 are
crystallographically independent as well as they have different co-ordination environments. The
Dy1 center shows nine coordination with ligation from three chelated carboxylates, two oxygen,
each from coordinated DMSO molecule and another oxygen from coordinated water molecule.
This gives an overall ‘spherical capped square antiprism’ with C4v symmetry (detailed geometric
analysis is described in section S7, ESI). On other hand, Dy2 is also nine coordinated with three
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chelated carboxylate, one bidentate carboxylate, one oxygen from coordinated DMSO molecule
and one from coordinated water molecule, thereby giving unique ‘muffin’ coordination sphere
with Cs symmetry as shown in Figure 3a. Two Dy2 atoms form a dimer through six carboxylate
groups of isophthalate ring in the ligand L2- in which four carboxylate rings extend the
dimensionality of the dimer into 1D chain (Figure 3b) through connecting Dy1 monomer units
and other two carboxylate rings extend the 1D chains in to 2D sheets through connectivity with
the Dy1 units of adjacent chains as shown in Figure 3c.
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Figure 3. (a) Different coordination spheres of Dy (III) metal atoms in assembly of compound 3;
(b) one dimensional zig-zag assembly of compound 3 (anthracene rings are omitted for clarity);
(c) 2D coordination network of compound 3 along ac plane. (d) Topological representation of
(3,6) network.
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The topological parameters of the structure were explained by reducing the Dy2-dimer to 6-
connected node and Dy1 monomer to 3-connected resulting in a (3,6) binodal network with kgd
topology (point symbol: {43}2{46.66.83}) (Figure 3d). The coordinated DMSO and water
molecules protrude into the void spaces provided by the 2D sheets. The organic part of the linker
i.e anthracenyl groups are hanged above and below the plane and cover the 2D sheets.
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Figure 4. (a) The Coordination environment of Dy2 dimer formed in compound 4; (b)
Representation of isophthalate connectivity of the linker (c) Representation of 1D zig-zag chain
projecting the coordinated DEF molecules.
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[{Dy(L)(DEF)}2(μ2-OH)]n (4). By employing the bulkier solvent molecule DEF the compound 4
crystallized in orthorhombic Pbcn space group. One deprotonated L2- ligand, and one Dy(III)
metal center, coordinated DEF molecule and μ2-OH constitutes the asymmetric unit. Here, the
Dy (III) metal centers are hexa coordinated and the metal center exists in ‘pentagonal pyramidal’
coordination sphere with C5v symmetry furnished by co-ordination from two bridging
carboxylates, one chelated carboxylate, one oxygen from coordinated DEF solvent molecule and
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bridging (μ2-OH) oxygen atom. Two Dy1 atoms are bridged by two carboxylate groups and μ2-
OH to form a Dy-dimer (Figure 4a). Each H2L connects two such dimers (Figure 4b) which
extends its dimensionality along only c axis to form 1D coordination polymer as shown in Figure
4c. One of the coordination site in the Dy(III) coordination sphere is occupied by the bulky
solvent molecule DEF which prevents formation of coordination sphere of higher number and
restricts the extension of 1D chains into 2D sheets contrary to above discussed structures. The
anthracenyl groups on the 1D chain are not arranged in a stacking configuration, indeed the
adjacent rings are perpendicular to each other.
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Figure 5. (a) Representation of 1D metal-oxide chain surrounded by aromatic moieties. (b)
Coordination environment of Dy (III) metal centers representing the square antiprismatic
coordination geometry. (c) One dimensional continuous channel along the crystallographic a-
axis. (d) Long range π···π interactions between the anthracenyl rings and phenanthroline rings in
compound 5
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[Dy2(L)3(phen)2·DMA·7H2O]n (5). By employing the chelating N-donor linker 1,10-
phenanthroline (phen) compound 5 was synthesized. Compound 5 crystallizes in monoclinic
system having C2/c space group. The asymmetric unit includes one Dy (III) atom, one and half
deprotonated L2-, one coordinated 1,10 phenanthroline (phen) ligand. The compound features a
1D chain extending along the crystallographic a axis in which the metal organic chains are
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buried under polyaromatic anthracenyl and phenanthroline rings (Figure 5a). Dy (III) metal
centers are octa coordinated. Four oxygen atoms each from four bridging carboxylates of four L2-
ligands, two oxygen atoms from one chelating carboxylate and two nitrogen atoms from
chelating phen molecule fulfill the coordination environment of metal centers as shown in Figure
5b. The coordination gives overall a ‘distorted square anti prismatic’ co-ordination geometry
with coordination symmetry D4d around the metal center (Table S1, ESI). The four bridging
carboxylates bridges the adjacent Dy(III) coordination spheres to form a Dy2 dimers of distorted
paddlewheel type geometry. Six L2- linkers involved in the formation of Dy2 dimers and the
isophthalate coordination connectivity of the linker connects these adjacent dimers to form a 1D
chain (Figure 5c). Long range π···π interactions within 3.904 Å was observed between the
anthracenyl rings and coordinated phen moieties of adjacent chains (Figure 5d).
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[Dy(L)(NO3)(py)2‧py]n (6). In continuation to employing N-donor linker in the reaction mixture,
we used pyridine (py) to obtain 6 which crystallizes in triclinic P-1 space group. One Dy (III)
metal atom, one deprotonated L2- ligand, two coordinated pyridine (py) molecules, one
coordinated nitrate ion and a guest py molecule constitute the asymmetric unit. This compound
features a 1D chain constituted by metal organic units with anthracenyl groups of the ligand and
coordinated py rings hanging above and below the chains.
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Figure 6. (a) Triangular dodecahedron coordination sphere constituted around Dy(III) metal
centers; (b) One dimensional continuous channel along the crystallographic a- axis.
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The coordination of ligand with the Dy(III) metal center forms a Dy-dimers in which each Dy
(III) center shows eight co-ordination, with ligation from two oxygen each from two bridging
carboxylates, two oxygen atoms from one chelated carboxylates, two oxygen atoms from one
coordinated nitrate ion and two nitrogen atoms each from two coordinated pyridine molecule (as
shown in Figure 6a). The overall coordination of linkers to the Dy(III) metal center results in the
‘triangular dodecahedron’ coordination sphere with D2d symmetry (the detailed geometric
analyses are described in section S7). The isophthalate coordination connectivity of the linker
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extend the dimensionality of the Dy2 dimers to form 1D chains along the crystallographic a axis
as shown in Figure 6b.
Comparison among the crystal structures
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Owing to the presence of three different functionalities (isophthalate connectivity, flexibility and
bulky anthracene chromophore) in the linker H2L as shown in the scheme 1, different
coordination assemblies are observed in the compounds 1-6. Lanthanide metal centers generally
exhibit higher coordination numbers 37 and in case of the compounds reported here Dy(III) metal
centers also adopt coordination numbers 8 and 9. The bulkiness of the linker and solvents are
accountable for the formation of lower dimensional (2D and 1D) rather than 3D structures in the
reported compounds. The compounds are categorized into two types, in which compounds 1, 2
and 3 display 2D coordination polymers, whereas 4, 5 and 6 feature 1D polymers. When the
metal coordination sphere contains relatively less bulkier solvents like DMF in 1, DMA in 2 and
DMSO in 3, they allow more linkers to coordinate with the metal center and thereby extend into
2-dimensional sheets (Figure 7).
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Figure 7. Figure indicating the coordination sphere of Dy(III) metal centers highlighting the
solvent and co-ligand coordination.
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On the other hand, the bulkiness of the solvents and N-donor linkers used in the reaction mixture
occupy the metal coordination spheres, and restricts the dimensionality to 1D in compounds 4, 5
and 6.38 The coordination of solvent molecules significantly influence the symmetry of metal
coordination sphere in the coordination polymers. By employing different solvent molecules,
different coordination spheres of the Dy(III) metal centers are obtained in the compounds,
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including the rare muffin coordination sphere as shown in section S7, ESI.39-40,23 Bharadwaj et al.
reported Gd-H2L coordination polymers in which different solvent dependent structural
transformation were observed.28 In these polymers the coordinated solvent was replaced by other
solvents to form different compounds where the coordination symmetry of metal center was not
altered to large extent. But in the present article it was observed that when the reaction was
performed in different solvents the coordination symmetry of the metal centers changes to a large
extent due to coordination of the solvents as well as the N-donor linkers (Figure 7).
The flexible (-CH2-NH-) group which is flanked between anthracenyl and isophthalate ring
offers the coordination flexibility to the linker to meet the coordination requirements imposed by
the solvent molecules used for crystallization.41 The anthracenyl unit twisted to different extents
with respect to isophthalate ring through a torsion angle (Canthryl-CH2-NH-Cisopthalte) ranges from
125° to 175° especially in compounds 1, 2, 3 and 5 whereas in compounds 4 and 6 these are
exactly perpendicular to the isophthalate rings (torsion angle is 180°). The change in orientation
of anthracenyl unit with respect to the isophthalate moiety in all the compounds were shown in
Figure 8a.
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Figure 8. (a) Projections of anthracenyl units with respect to isophthalate moiety of H2L linker in
compounds 1-6 (b) Representative coordination modes exhibited by the linker H2L in
compounds 1-6.
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The presence relatively less bulkier solvents DMF in 1, DMA in 2, DMSO in 3 and chelating
linker phen in 5 may be responsible for twisting of anthracenyl units to different extents.
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However, it was observed that presence of bulkier solvent DEF in 4 and py in 5 restricts the
rotation of the anthracenyl group in the linker. The linker L2- exhibits four different types of
coordination modes in the compounds as shown in the Figure 8b.42
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PXRD and Thermal analysis
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To confirm the phase purity of the stable compounds (1-6) presented in this study, X-ray
diffraction patterns of powder samples have been recorded. The reflections for the simulated data
(calculated from single crystal data) are well matched with the observed data, which proves the
bulk homogeneity of the crystalline solids (See section S4 of supporting information). Some
reflections are slightly broadened in the experimental pattern as compared to simulated data.
Thermal stability of the compounds was studied from TGA curves which are recorded
under N2 flow from room temperature to 600 °C as shown in Section S5, ESI. Compound 1
exhibits thermal stability up to 330 °C with weight loss of 1.45 % (theoretical weight loss 1.34
%) corresponding to solvent water which was then undergoes continuous decomposition
attributed to the, coordinated DMF, dimethylammonium cation and organic part of the linker.
Compound 2 shows weight losses of 4.70 % (theoretical weight loss 4.06 %) equivalent to the
lattice and coordinated water molecules up to 150 °C, and 15.34 % (theoretical weight loss 14.77
%) up to 330 °C corresponding to lattice and coordinated DMA molecules. A Sharp weight loss
was observed in the region 330- 450 °C, which can be the decomposition of linker. Compound
3 undergoes initial weight loss of 13.15 % (theoretical weight loss 12.03 %) up to 325 °C related
to lattice DMSO and H2O molecules along with coordinated H2O molecules. The residual
compound undergoes gradually weight loss of the coordinated DMSO molecules and organic
linker. The continuous decomposition of coordinated DEF molecules in compound 4 was
observed till 300 °C with weight loss of 17.4 % (theoretical weight loss 15.46 %) and a sharp
decrease of 33% weight loss corresponding to the linker occurred by increasing temperature.
Compound 5 remains thermally stable up to 369 °C with weight loss of 6.3 % which nearly
corresponds to the solvent water molecules (Theoretical weight loss of 6.36 %) and undergoes
stepwise decomposition of lattice DMA and organic linkers at higher temperatures. Initial weight
loss of 31.2 % (theoretical weight loss 28.11 %) corresponding to the coordinated and lattice
pyridine molecules in compound 6 was observed till 342 °C followed by sharp decomposition of
linker in the interval of 20 °C. The compounds (1-6) display thermal stability up to 330 °C and
undergoes continuous decomposition of organic linkers to gives the residue of metal oxides.43-44
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The luminescence of lanthanide ions due to f-f transitions are parity allowed magnetic dipole and
parity forbidden electric dipole transitions.45 These transitions are sensitive to the local chemical
environments of the metal centers. The chemical environment around the Dy(III) centers in the
compounds 1-6 significantly varies corresponding to the symmetry of the coordination sphere
and greatly influence the emission behaviors of the compounds.
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The solution state emission spectrum of the linker H2L, displays sharp emission bands at 417,
440 and 464 nm (Figure S7, Section S6). The literature studies show that the emission at 417 is
attributed to ligand centered emission whereas the other two peaks at 440 and 464 are related to
the vibrational structure.29 Whereas, the solid-state emission spectra of the linker H2L shows a
broad band with emission maxima at 452 nm indicates the ligand centered emission due to π*-π
transitions from anthracene ring (Figure 9).28 The solid state spectra of Dy(III) compounds (1-6)
show broad absorption bands in the region 460-560 nm upon excitation at 396 nm (Figure 9).
Compound 1 in which DMF is coordinated to the Dy(III) metal center which resides in D2d
coordination sphere show emission band at 499 nm. Compound 2 also show similar emission
profile in which DMA is coordinated and displays emission maxima at 495 nm. Compound 2
contains four Dy(III) centers in which three exists in C2v and other in D4d coordination sphere.
The emission maxima were shifted to 473 nm with two shoulder peaks at 423 and 451 nm in
compound 3 where DMSO is coordinated. The shoulder peaks at 423 and 451 nm may be due to
incomplete transfer of energy from the linker to metal center.46 The symmetry of the
coordination sphere around metal center in 3 are C4v and rare muffin Cs symmetry. By
employing relatively bulkier solvent DEF in compound 4 the emission maxima were observed at
466 nm in which metal center resides in C5v symmetry. The emission profile of the compound 5
where the chelated linker phen was employed is completely different from other compound
spectra.47 Compound 5 exhibits emission bands with emission maxima at 410 nm and three low
intense relatively sharp peaks centered at 467, 482 and 493 and very small shoulders around 580
and 650 nm. The peaks 482 and 580 can be assigned to characteristic emissions of 4F9/2 → 6HJ (J
= 15/2, 13/2) transitions exhibited by the Dy(III) ion.48 When py was employed as coordinating
solvent the emission maxima was largely blue shifted to 560 nm in compound 6 compared to all
other compounds along with the peak at lower wavelength 423 nm. The peak at 423 nm can be
attributed to the incomplete energy transfer from the linker to metal center. The emission at 560
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nm in compound 6 can be related to the characteristic emission of F9/2 → H13/2 transition of
Dy(III) metal centers. The coordinated solvent molecules in 1-4 and chelated linker in 5 and 6
significantly shifts the emission maxima either due to the electronic effects induced by the
solvent molecule or due to the coordination symmetry expressed by the metal centers.49 More
systematic studies are required to better quantify the emission characteristics of these polymers.
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Figure 9. Solid state emission spectra of the linker and compounds 1-6 (left) and tabular form
representing the emission parameters (Right).
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Conclusion
The article highlights the influential role of solvent molecules/N-donor co-ligands in obtaining
diverse Dy(III) coordination spheres in the coordination polymers constructed by using flexible
isophthalate linker H2L. Six lanthanide coordination polymers 1-6 were synthesized and
structurally characterized by employing the Dy(III) salt and H2L in presence of different bulkier
solvents DMF, DMA, DMSO, DEF and N-donor linkers phen and py. When metal center is
coordinated with relatively less bulkier solvents DMF, DMA and DMSO in compounds 1, 2 and
3 respectively, Dy(III) metal centers exhibits higher coordination numbers 8, 9 and the
dimensionality of the compounds are extended to 2D sheets. The coordination of bulkier DEF
molecule in 4 reduces the coordination number of the Dy(III) to 6 and restricts the
dimensionality to 1D chains. The chelating nature of the phen blocks the extension of metal
coordination sphere and reduces the dimensionality to 1D chains in compound 5. In a similar
way in compound 6 the bulkier coordinated solvent molecule py also reduces the dimensionality
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to 1D chains. We were able to isolate Dy(III) coordination spheres with different symmetries
(D2d in 1, C2v and D4d in 2, C4v and Cs in 3, C5v in 4, D4d in 5 and D2d in 6) by changing the
bulkiness of the solvent molecules in the corresponding coordination polymers. The
photoluminescent studies of these polymers reveals that emission behaviors are significantly
dependent upon the coordination symmetries expressed by Dy(III) metal centers in their
corresponding coordination polymers. Overall, the work presented in this article provides the
promising strategy to obtain coordination polymers with different metal coordination symmetries
under the influence of solvent molecules, which consecutively tune the emission properties of the
materials. Similar strategies are underway to better understand the influence of coordination
symmetry of metal center in the coordination polymer on the emission behavior.
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Associated Content
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI:
10.1021/acs.cgd.0000000. Synthesis and characterization of linker, Asymmetric units of
compounds, PXRD, TGA, emission spectra of H2L, Details of coordination parameters, Details
of Shape analyses.
Accession codes
CCDC 1947677 (Compound 1), 1947679 (Compound 2), 1947680 (Compound 3), 1947678
(Compound 4), 1947681(Compound 5) and 1947676 (Compound 6) contains the supplementary
crystallographic data for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by
contacting The Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ,
UK, fax:+44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: nithi.phukan7@gmail.com
*E-mail: aryanbharat@gmail.com
ORCID
Bharat Kumar Tripuramallu: 0000-0002-3859-4364
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Soumyabrata Goswami: 0000-0002-9646-1439
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Notes
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This research was supported by the Israel Science Foundation (grant no. 108/12). Our special
thanks are due to Yoel Friedman for recording TGA data.
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Title: Solvent Influence in Obtaining Diverse Coordination Symmetries of Dy(III) Metal Centers
in Coordination Polymers: Synthesis, Characterization and Luminescent Properties
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Authors: Nithi Phukan,*a Soumyabrata Goswami,b Sophie Lipstman,a Israel Goldberg,a and
Bharat Kumar Tripuramallu*c
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TOC
Synopsis
Influential role of bulkier solvents in obtaining diverse symmetries of Dy(III) metal coordination
sphere in the coordination polymers constructed by employing flexible linker were discussed in
the article. The Dy(III) coordination spheres sensitizes the emission behavior significantly in the
compounds reported in the article .
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