Synthesis, crystal structure, and two-dimension correlation infrared spectroscopy on two novel Pr carboxylic acid coordination polymers

Accepted Manuscript Synthesis, crystal structure, and two-dimension correlation infrared spectroscopy on two novel Pr carboxylic acid coordination polymers

Lingyan Zhao, Yiping Chen, Yunjing Hao, Pingping Ma, Ning Wang, Hengbing Hu PII: DOI: Reference:

S1386-1425(19)30060-5 https://doi.org/10.1016/j.saa.2019.01.055 SAA 16741

To appear in:

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Received date: Revised date: Accepted date:

11 July 2018 1 December 2018 15 January 2019

Please cite this article as: Lingyan Zhao, Yiping Chen, Yunjing Hao, Pingping Ma, Ning Wang, Hengbing Hu , Synthesis, crystal structure, and two-dimension correlation infrared spectroscopy on two novel Pr carboxylic acid coordination polymers. Saa (2019), https://doi.org/10.1016/j.saa.2019.01.055

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ACCEPTED MANUSCRIPT

Synthesis, crystal structure, and two-dimension correlation infrared spectroscopy on two novel Pr carboxylic acid coordination polymers

College of Qian’an, North China University of Science and Technology, Qian’an, Hebei,

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Lingyan Zhao,*1 ,Yiping Chen2,Yunjing Hao1 , Pingping Ma1 , Ning Wang1 , Hengbing Hu2

Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002, P.R. China

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064400, P. R. China

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* Corresponding author. Tel: +86-0315-6336344

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*E-mail: [email protected]

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Abstract

Two new coordination polymers [Pr(PCPA)3(H2O)]n

1 and [Pr2(PCPA)6(H2O)3]n·nH2O

2(PCPA= p-chlorophenoxyacetic acid) have been synthesized under similar conditions by the

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hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analyses, powder X-ray diffraction (PXRD) analysis, IR spectroscopy, two-dimensional

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correlation infrared spectroscopy(2D-IR COS) and ultraviolet-visible diffuse reflection integral spectroscopy (UV-vis DRIS). 1 displays a 1D infinite chain, which is further linked by O/C-H···O hydrogen bonds to form a 3D supra-molecular architecture. 2 shows a 2D layer structure, which is extended by C-H…Cl hydrogen bonds generating a 3D network. Noteworthy, we also studied 2D-IR COS under the thermal perturbation to contribute to the development of theory. The 2D-IR correlation spectroscopy analysis is consistent with the analysis of structure and it is superior to 1D IR spectroscopy especially in the coordinated carboxyl group.

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ACCEPTED MANUSCRIPT Keywords: p-chlorophenoxyacetic acid; Pr(III) coordination polymers; synthesis reaction condition; 2D-IR COS spectroscopy

1.Introduction

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The crystal engineering of metal-organic frameworks (MOFs) has been becoming a more

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and more popular research field. The reasons are not only due to their intriguing structural

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topologies but fascinating properties such as heterogeneous catalysis[1-2], molecular absorption[3-4], molecular sensors [5], non-linear optical (NLO) materials[6] as well as the

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applications in the electrical area [7-8], magnetic area[9], photochemical area [10]，biological

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probe[11], and so on. Actually, the research of metal-organic frameworks (MOFs) with the above-mentioned novel properties remains a significant challenge for chemists. As is well

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known to us all, the structure of coordination polymer decides its property and plays an

ligands

(main

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important part in the application. In fact, many factors such as metal ions [12-13], organic ligands

solvent

ancillary

ligand)[14-16],

preference[20-22],

pH

metal/ligand value[23-24],

ratios[17], reaction

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counter-anions[18-19],

and

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temperature[25-26], reaction time[27], synthetic methods[28] and so on[29-30] influence the final structures of coordination polymers. The choices of metal ions and organic ligands have an important influence on the final structures of coordination polymers in those factors. At the same time, the construction of novel architecture sometimes needs supra-molecular interactions. Compared with the coordination bonds, supra-molecular interactions including hydrogen bond[31], C-H∙∙∙π[32], C-H∙∙∙Cl[33] and π∙∙∙π stacking interactions[34-36], metal-metal interaction[37-38]and weak coordinative interaction[39]etc. can construct all

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ACCEPTED MANUSCRIPT kinds of novel topologies and potential application in host-guest chemistry, catalysis, etc[40]. Taking the most advantage of the afore-mentioned factors, we select the rare-earth ion having large radii and high coordination-number and flexible aryl-carboxyl ligand having abundant coordination modes—p-chlorophenoxyacetic acid (PCPA) and fortunately obtain

1 and [Pr2(PCPA)6(H2O)3]n·nH2O 2.

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hydrothermal condition, namely, [Pr(PCPA)3(H2O)]n

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two novel coordination polymers having the same composition and different structures under

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In order to further investigate the relationship between the structure and property, two compounds are characterized by XRD, elemental analyses, powder XRD analysis, IR

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spectroscopy, UV-vis DRIS spectroscopy. Meanwhile, in order to clarify the spectral feature,

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2D-IR correlation spectroscopy was applied with thermal perturbation. It is worth mentioning that the conformational change of the bond Ar-O-C of PCPA plays a significant role in the

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formation of hydrogen bond by the structure analysis. Moreover, 2D-IR correlation

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spectroscopy analysis indicates that there are two different induction peaks from the asymmetric stretching vibration and symmetric stretching vibration of C=O in the carboxylate

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groups due to having two kinds of coordination modes for the carboxylate group of PCPA in

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1 and 2，which didn’t be shown in the 1D IR.

2. Experimental

2.1. Materials and Physical Methods

Commercially available solvents and chemicals used in this work were purchased from Sinopharm Group Company and were used without further purification. IR spectra were 3

ACCEPTED MANUSCRIPT measured as KBr pellets on a Perkin-Elmer Spectrum 2000 FT-IR in the range 400-4000cm-1. The elemental analyses of C, H, and N were carried out on an Elementar Vario EL III elemental analyzer. Powder X-ray diffraction (PXRD) patterns were recorded on an X’pert Pro diffractometer(CuKα) at room temperature. UV-Vis DRIS spectra were measured in the

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range of 200–800 nm on Perkin-Elmer Lambda 900 UV/Vis spectrometer.

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2.2. Synthesis of [Pr(PCPA)3(H2O)]n 1 and [Pr2(PCPA)6(H2O)3]n·nH2O 2

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1 was prepared by hydrothermal reaction. A mixture of Pr(NO3)3·6H2O(0.25mmol, 0.109g), PCPA (0.30mmol, 0.056g), NaOH (0.30mmol, 0.12g), H2O (10mL) and pH=6.1 was sealed

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into a bomb equipped with a teflon liner, heated at 393 K for 72 hours and then cooled to room temperature. Light green rod-like crystals were obtained. Elemental Analytical.

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Calculation.C,40.24 ;H,2.79; O, 22.36%. Found: C,40.04 ; H,2.66; O,22.10 %. 2 was prepared by hydrothermal reaction. A mixture of Pr(NO3)3·6H2O(0.25mmol, 0.109g),

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PCPA (0.50mmol, 0.093g), NaOH (0.50mmol, 0.02g), H2O (10mL) and pH=5.9 was sealed into a bomb equipped with a teflon liner, heated at 393 K for 48 hours and then cooled to

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room temperature. Light green sheet crystals were obtained. Elemental Analytical. Calculation.C,39.25;H,3.00; O, 23.99%. Found: C, 39.01; H,2.86; O,23.79 %.

2.3. X-ray Crystallography

Suitable single crystals of 1 and 2 were mounted on glass fibers for X-ray measurement. Reflection data were collected at room temperature on a Rigaku Saturn 724 CCD 4

ACCEPTED MANUSCRIPT diffractometer with graphite monochromatized MoKα radiation (λ= 0.7107 Å). Crystal structures were solved by the direct method and refined by full-matrix least-squares techniques against F2 using the SHELX XS-97[41(a)] crystallographic software package. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were fixed at calculated

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positions and refined by using a riding mode. All calculations were performed using the

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SHELXTL-97[41 (b)] program. The Crystal data for 1 and 2 were given in Table 1. Selected

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bond lengths and bond angles of 1 and 2 were listed in Table S1 and Table S2.

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Insert Table 1

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3. Results and Discussion

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3.1. Structural description of [Pr(PCPA)3(H2O)]n

The X-ray crystal structure analysis reveals that 1 is a 1D infinite chain, crystallizing in

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triclinic space group P-1. The asymmetric unit contains one Pr(III) ion, three PCPA anions,

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one coordinated water molecule(Fig.1). The nine-coordinated Pr(III) ion can be described as three-cap triangular prism configurations with the equatorial positions occupied by eight oxygen atoms from six PCPA anions and one oxygen atom from the coordinated water molecule. The Pr-O bond lengths are 2.445-2.5769Å, which are comparable to those in other Pr (III) compounds containing carboxylate groups[42-46]. As shown in Fig.2, the carboxylate groups of PCPAs show two coordination modes, namely, bidentate chelating and unidentate bridged µ2-η1:η2 and bidentate bridged µ2-η1:η1. Two adjacent Pr ions are connected by two

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ACCEPTED MANUSCRIPT bidentate chelating and unidentate bridged carboxylate groups and two cis-cis bidentate bridged carboxylate groups and come into being a 1D infinite chain. Insert Fig.1 Insert Fig.2

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In order to conveniently draw and discuss the structure of 1, we center on the Pr ion to

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draw the Pr-O polyhedron (Fig.3a) and designate those coordinated PCPAs as

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α,α*,β,β*,γ,γ*(Fig.3a). As is shown in Fig.3, there are the π…π stacking interactions between β and γ and β*and γ*, the central distance of Cg1 ring to Cg2 ring is 3.731Å

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(Cg1:C1-C2-C3-C4-C5-C6,Cg2:C9-C10-C11-C12-C13-C14). There exists O-H···O hydrogen bond

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between O9 and H10a (dist(O10···O9)= 2.9726(8) Å). Specifically, the coordinated water molecule has two hydrogen atoms H10a and H10b and only hydrogen atom H10a forms the

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hydrogen bond, which is demonstrated in the IR spectra.

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Insert Fig.3

As Fig. 4a is shown that the 1D chain are tightly lined with the hydrogen interactions into

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the layer structure in the a-b plane, namely, C6-H6···O4 (dist(C6···O4)= 3.192(4) Å) between β

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and β* and O-H···Cl (dist(O10···Cl1)= 3.1665(8) Å) between the Cl atoms of γ and γ* and O atoms of the coordinated H2O, and that those data are in agreement with the reported literatures[47-48]. It is noteworthy that conformational change of the bond Ar-O-C of PCPA plays the significant roles in the formations of above-mentioned hydrogen bonds. As is shown in Fig.4b, for the B chain, the bond angle of
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3D supra-molecular architecture is formed by the O/C-H···O hydrogen bonds between those

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PCPAs(Fig.5). The parameters of hydrogen bonds and aromatic-aromatic are shown in Table

Insert Fig.4

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Insert Fig.5

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S3.

2

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3.2.Structural description of [Pr2(PCPA)6(H2O)3]n·nH2O

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The X-ray crystal structure analysis reveals that 2 is a 2D layer structure, crystallizing in

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triclinic crystal system with space group P-1. There are two Pr ions, six PCPA anions, three coordinated water molecules and one uncoordinated water molecule in the asymmetric unit

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(Fig.6). The coordination numbers of Pr1 and Pr2 are both eight and trigonal dodecahedron

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configuration. The Pr1 ion coordinates with seven oxygen atoms from six PCPA anions and one oxygen atom from one coordinated water molecule, The Pr2 ion coordinates with six oxygen atoms from six PCPA anions and two oxygen atoms from two coordinated water molecules. The Pr-O bond lengths are 2.374-2.675Å, which are in good agreement with those in other Pr ion compounds containing carboxylate groups[42-46]. As shown in Fig.7, the carboxylate groups of PCPAs also show two coordination modes, namely, bidentate chelating and unidentate bridged µ2-η1:η2 and bidentate bridged µ2-η1:η1. Two adjacent Pr ions are

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ACCEPTED MANUSCRIPT connected into a 1D infinite chain by the bridged carboxylate groups of PCPAs. Insert Fig.6 Insert Fig.7 The adjacent chains are linked into 2D layer structure by the bidentate bridged carboxylate

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groups of PCPAs(Fig.8a). Moreover, there exist π···π stacking interactions between the

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adjacent chains and the central distance of Cg4 and Cg5 is 3.947 Å(Cg4:

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C1-C2-C3-C4-C5-C6, Cg5: C17-C18-C19-C20-C21-C22) (Fig.8b). Meanwhile, the C-H…π interactions and hydrogen bonds exist between two sides of coordinated PCPAs in the layer

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structure. The layer structures stack along the c axis by the weak interaction of C-H…Cl

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hydrogen bond (dist(C30…Cl2)=3.8432(12)Å) (Fig.9)and form into 3D supra-molecule architecture. The parameters of hydrogen bonds and aromatic-aromatic are shown in Table S4.

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Insert Fig.8

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Insert Fig.9

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3.3.Influence of the synthesis reaction conditions on the structures of compounds

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As illustrated above, the reactants synthesized the 1 and 2 are same and the compositions of final products-[Pr(PCPA)3(H2O)]n 1 and [Pr2(PCPA)6(H2O)3]n·nH2O 2 are also same. The difference of two complexes is the quantities of the compositions and this finally leads to the difference of their structures. As far as we known that the systematic pH plays an important role in the formation of compound and it can make the organic ligands adopt the different coordination mode[24]. In this paper, the reason is that the synthesis reaction conditions of 1 and 2 are different, namely, the pH is 6.1 for 1 and 5.9 for 2. Moreover, the molar ratio of PCPA and

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ACCEPTED MANUSCRIPT Pr(NO3)3·6H2O is 6:5 for 1 and 10:5 for 2. The reaction system of 2 contains more PCPA and it

makes the pH of its solution lower. Namely, the acidity of reaction system 2 is higher, which makes the extent of Pr ion hydrolyzation small. So there are more Pr ions in 2 and the ligand-PCPA has more opportunities to coordinate. Furthermore, the pH value of reaction

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system 1 is higher and the degree of deprotonation of the carboxylic group is stronger, the

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coordination modes of the carboxylic group of PCPA in 1 contain bidentate chelating and

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unidentate bridged µ2-η1:η2 and bidentate bridged µ2-η1:η1, which connected two Pr ions to the 1D chain. Thus, the synthesis reaction conditions play a significant role in the structures of

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complexes.

3.4 PXRD analysis

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The observed and simulated powder XRD patterns of 1 and 2 are depicted in Fig.1s. It is obvious that the measured powder XRD pattern is in good agreement with the pattern

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simulated from the X-ray single crystal data, indicating phase purities of the sample. The difference in reflection intensities between the simulated and experimental patterns is due to

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the different orientation of the crystals in the bulk powder sample [49].

3. 5. 2D correlation analysis of FTIR

The FTIR spectra of 1 and 2 are shown in Fig. 2S and the assignments of the main absorption peak are listed in table S5 [50-54] The generalized 2D COS spectroscopy proposed by Noda[55-57] is a very useful tool to 9

ACCEPTED MANUSCRIPT clarify subtle spectral changes. The 2D-IR COS spectroscopy contains two kinds of spectrograms, that is synchronous and asynchronous spectra. In the synchronous spectra, the correlation peak in the diagonal line is auto peak and it shows the result of autocorrelation analysis of the same vibration peak of the same group. In the case of an external perturbation,

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the electric transient dipole moment of the group is easy to change, which indicates that the

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peak is stronger. The cross peak indicates that the relationship between the change trend of the

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electric transient dipole moment of the different groups under external perturbation. In this paper, thermal-induced 2D-IR COS spectroscopy is used to investigate the structures of title

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compounds[58].

Insert Fig.10

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Insert Fig.11

2D-IR COS spectroscopy under thermal-induced changes of 1 and 2 are respectively shown

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in Fig.10.and Fig.11. In the synchronous spectra of 1 in Figure 10a, two obvious inductions appear from 3300 to 3700 cm-1. Peaks at 3641 cm-1, 3450 cm-1and 3399 cm-1 are assigned to

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thermal-induced stretching vibrations of O-H of unformed hydrogen bond H2O, PCPA and formed hydrogen bond H2O respectively. Moreover, the intensity of autopeak at 3399 cm-1 is

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stronger, which indicates that stretching vibrations of O-H of formed hydrogen bond H2O is more sensitive to the thermal perturbation. The positive cross-peaks at (3399, 3450) cm-1,(3399, 3641) cm-1 reveal that the direction of these bands intensity changes is consistent. In the synchronous spectra of 2 in the Figure 11a, due to also exist two kinds of O-H, there appear two induced peaks at 3440 and 3350 cm-1 belonging to thermal-induced stretching vibrations of O-H of the coordinated water molecule and uncoordinated water molecule respectively for 2 in the range of 3300-3500 cm-1. The positive cross-peak at (3350, 3440) 10

ACCEPTED MANUSCRIPT cm-1 reveals that the direction of these bands intensity changes is consistent. In Figure 10b,there is the evident induction to the thermal perturbation from 2920 to 3100 cm-1 for 1: the very strong peak at 3070 cm-1 should be the characteristic peak for the thermal-induced stretching vibration of =C–H in benzene ring and two different induced

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peaks at 2920 and 2980 cm-1 should correspond to two different states asymmetric stretching

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vibrations of –CH2–, that is because the flexibility of phenoxy oxygen bond makes

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methylene-–CH2– come into being the different conformation to form the hydrogen bond. The intensities of response peaks indicate that the stretching vibrations of =C–H in aromatic rings

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are more sensitive to the thermal perturbation, the reason should be that the π···π stacking

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interactions between the aromatic rings and the C-H···O and C-H···Cl hydrogen bonds formed the unsaturated hydrogen atoms of aromatic rings are very sensitive to the thermal

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perturbation, those hydrogen bonds and weak interactions make the induction conduct to the

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stretching vibrations of =C–H in aromatic rings when the temperature changes, which make the stretching vibrations of =C–H in aromatic rings sensitive to thermal perturbation. What is

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noteworthy is that the response peaks of compound 2 are different from compound 1. In

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Figure 11b, there is a very strong response peak at 2920 in the synchronous spectrum from 2900 to 3100 cm-1 and it is assigned to the asymmetric stretching vibrations of –CH2–. νas (–CH2–) is extremely sensitive to thermal perturbation and the intensity of its response peak is great so that the ν (=C–H) response peak at 3060 cm-1 isn’t found. It indicates that compared with νas (–CH2–) of 1, νas (–CH2–) of 2 is more sensitive to thermal perturbation, that may be because that the hydrogen atom of –CH2– in 2 as the donor forms C7-H7b···O17 hydrogen bond, then the hydrogen bond makes the induction to the temperature variation conduct to the

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ACCEPTED MANUSCRIPT –CH2–. As is shown in Fig.10c, it appears the obvious induction from 1400 to 1640 cm-1. We can see clearly that in the synchronous spectrum there are evident response double peaks at 1494 and 1480 cm-1, 1427 and 1415 cm-1, 1585 cm-1which are respectively assigned to two kinds of

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the symmetric and asymmetric stretching vibrations of the carboxylate groups and benzene

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skeleton vibration. The reason why there appear two kinds of stretching vibrations of the

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carboxylate groups is that the carboxylate groups of PCPAs have two coordination modes in 1, namely, one is bi-dentate chelating and uni-dentate bridged µ2-η1:η2 and the other is bi-dentate

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bridged µ2-η1:η1, However, those aren’t indicated in the 1D-IR spectra, which is not only

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consistent with the structural analysis but also give full expression to the main advantage of 2D-IR COS. The positive cross-peak at (1415, 1427) cm-1, (1415, 1480) cm-1 reveals that the

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direction of these bands intensity changes is consistent. In Figure11c, 2 has similar response

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peaks from 1150 to 1640 cm-1. In addition, the medium-intensity response peak at 1234 cm-1 and 1590 cm-1belongs to the stretching vibration of Ar-O-R and benzene skeleton vibration

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respectively, the autopeak at 1234 cm-1 indicates that the flexible joint of PCPA has the larger

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distortion with the change of the temperature and makes further verify the flexible ligand characteristic of PCPA. The positive cross-peak at (1234, 1493) cm-1, (1234, 1590) cm-1 reveals that the direction of these bands intensity changes is consistent [16,21,59].

3.6. UV–VIS DRIS spectrum

In UV-Vis spectrum of 1 (Fig.12), it shows a strong band centered at 288nm, which can be assigned to Π-Π* electron transition absorption peak of ligand. It is illustrated that PCPAs 12

ACCEPTED MANUSCRIPT coordinated Pr(III) ions have no influence on the π → π* transit of its benzene rings. In addition, there exist the characteristic absorption peaks at 444nm, 470nm, 483nm, and 597nm, which correspond to the transitions from 3H4→3P2, 3H4→3P1, 3H4→3P0 and 3H4→1D2 respectively for Pr(III) ion[60].

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Insert Fig.12

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4. Conclusions

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In a word, two novel coordination polymers consisting of Pr(III) ion and PCPA had been

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successfully synthesized in the hydrothermal synthesis condition. The structures analyses indicate that the asymmetric unit of 1 contains one nine-coordinated Pr(III) ion and 1 shows a

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1D infinite chain, while the asymmetric unit of 2 contains two eight-coordinated Pr(III) ion

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and 2 shows a 2D layer structure. Meanwhile, the flexible joint of PCPA, namely of Ar-O-R plays an important role in the formation of the hydrogen bond, which had been proved by the

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analysis of 2D-IR COS spectroscopy. The analysis of 2D-IR COS spectroscopy shows that the

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carboxylate groups of PCPAs have two coordination modes, namely, bidentate chelating and unidentate bridged µ2-η1:η2 and bidentate bridged µ2-η1:η1, which is in accordance with the analysis of structures. However, those aren’t detected in the 1D-IR spectra, which is not only consistent with the structural analysis but also give full expression to the main advantage of 2D-IR COS.

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ACCEPTED MANUSCRIPT Acknowledgments

The authors are grateful for the financial support from the Undergraduate Training Program

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for Innovation and Entrepreneurship (X2018268)

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ACCEPTED MANUSCRIPT [59] Y.P.Chen, H.H.Zhang, C.C. Huang,Y.N. Cao, R.Q. Sun, W.J. Guo, Synthesis and two-dimensional correlation infrared spectroscopy studyof an organic–inorganic hybrid compound constructed by [Mo5P2O23]and Cu-imidazole components. Spectrochim. Acta. A, 63 (2006) 536–540. [60] M. Shahida*, A. Siddiquea, M. Ashafaqa, M.Raizadaa, F. Samaa, M. NaqiAhamada, M. I.a, I. A. Ansaria, I. M. Khana, P. Kumarb*, K. Fatmaa, Z. A. Siddiqia,Spectroscopic

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Luminescence properties and biological activities, J. Mol. Struct, DOI:

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Table 1 Crystallographic data for 1 and 2. Compounds

2

C24H20Cl3O10Pr

C48H44Cl6O22Pr2

Formula weight

715.66

1467.35

Temperature / K

293

293

Wavelength / Å

0.7107

0.7107

Crystal system

Triclinic

Space group

P-1

a/Å

7.9603(16)

b/Å

12.712(3)

c/Å

14.009(3)

21.182(4)

/

80.92(3)

95.66(3)

/

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P-1

11.430(2)

11.570(2)

78.68(3)

95.66(3)

76.34(3)

93.29(3)

1341.4(5)

2767.5(10)

2

2

Dcalc / g . mˉ3

1.747

1.761

Crystal size / mm3

0.43 × 0.29 × 0.28

0.42×0.21×0.11

Reflections collected

8508

15735

Independent reflections ( Rint)

5777 (0.0265)

8139 (0.0258)

R indices ( I >2σ (I))

R1= 0.0320, wR2 = 0.0894

R1=0.0598, wR2=0.1913

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R1= 0.0323, wR2= 0.0898

R1=0.0676, wR2=0.1991

w(1) = 1/[σ2(Fo)2 + (0.0231P)2 +0.5290P], P = (Fo2+2Fc2)/3;

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w(2) = 1/[σ2(Fo)2 + (0.0954P)2 + 4.5938P], P = (Fo2+2Fc2)/3.

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Fig.3. Polyhedron drawing of the π-π weak interactions and hydrogen bonds on the 1D chain for 1 (a); the polyhedron drawing of the 1D chain for 1 along an axis (b).

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Fig.12. UV-Visible absorption spectra of 1 and Pr(III)ion.

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ACCEPTED MANUSCRIPT Graphical Abstract The synchronous 2D correlation FTIR spectra for 2 in the range of a:3300–3500 cm-1;

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Synthesis, crystal structure, and two-dimension correlation infrared spectroscopy on two novel Pr carboxylic acid complexes Lingyan Zhao*1, Yiping Chen2,Yunjing Hao1, Pingping Ma1, Ning Wang1, Hengbing Hu2 College of Qian’an, North China University of Science and Technology, Qian’an, Hebei,

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Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002, P.R. China

* Corresponding author. Tel: +86-0315-6336344

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*E-mail: [email protected]

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064400, P. R. China

I am a pleasure to submit the enclosed manuscript entitled “Synthesis, crystal structure,

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and two-dimension correlation infrared spectroscopy on two novel Pr carboxylic acid coordination polymers”, which we wish can be considered for publication in Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy.

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The highlights are listed as followed:

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1. Two Pr/p-chlorophenoxyacetic acid compounds have been synthesized under similar

conditions by hydrothermal method. 2. The different synthesis reaction conditions lead to the different structures of 1 and 2.

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been studied.

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3. The influence of synthesis reaction conditions on the structure of compound 1 and 2 have

4. 2D-IR correlation spectroscopy and UV-vis DRIS spectroscopy for compound 1 and 2 are

studied.

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