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doi: 10.1007/s11426-012-4595-9 doi: 10.1007/s11426-012-4595-9

Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline
WANG JuanFen1, LI Hua2, ZHANG JianJun1*, REN Ning3 & WU KeZhong1
1

Experimental Center, Hebei Normal University, Shijiazhuang 050016, China 2 Shijiazhuang College, Shijiazhuang 050035, China 3 Department of Chemistry, Handan College, Handan 056005, China Received December 1, 2011 ; accepted Feburary 11, 2012

This paper describes syntheses and structure determination of four lanthanide complexes [Nd(2-Cl-4-FBA)3phen]2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), [Ln(2,5-DClBA)3phen]2 (Ln = Sm(2) and Tb(3), 2,5DClBA = 2,5-dichlorobenzoate) and [Sm(2-Cl-4,5-DFBA)3(phen)(H2O)]2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzoate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 14, two Ln3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H2O molecule. There are two different coordination polyhedrons for each Nd3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln3+ ion in 24 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the non-isothermal kinetics of 14 by the integral isoconversional non-linear (NL-INT) method. rare earth complexes, thermal decomposition mechanism, crystal structures, three-dimensional IR accumulation spectra, evolved gases, TG/DSC-FTIR, non-isothermal kinetics

1 Introduction
Currently, lanthanide carboxylate complexes have attracted increasing attention, due to their unique and various structures [17] and practical applications, such as in ion-exchange, catalysis, separation [8], and as luminescent materials [912] and bacteriostatic agents [1315]. In addition, thermal analysis techniques have been further devel*Corresponding author (email: jjzhang6@126.com) Science China Press and Springer-Verlag Berlin Heidelberg 2012

oped and widely used to study the thermal properties of solid materials. These studies provide valuable information for their potential applications. For this purpose, the TG/ DSC-FTIR technique conducting simultaneous and continuous real time analysis [1618] is used to study the thermal decomposition mechanism of the complexes, which provides more information about the relevant gaseous products. In view of the potential applications and as a continuation of our work on the lanthanide carboxylate complexes, in this paper, we have synthesized four new lanthanide complexes

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with different halogen-benzoic acids and 1,10-phenanthroline and their single crystals have also been obtained. The center Ln3+ ions in the complexes are all nine-coordinated. The complexes 2 and 3 which have identical ligands are isostructural. It is noted that two bonding water molecules exist in the structure of the complex 4, which may be due to the steric effect caused by the more halogen substituents in the benzoic acid ligand. Furthermore, the thermal properties and non-isothermal kinetics of the four complexes were studied. The 3D surface FTIR spectra graphs of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs.

2 Experiment
2.1 Materials

All reagents and chemicals were of analytical purity and used as supplied. LnCl36H2O were prepared by dissolving their respective oxide in hydrochloric acid, and then drying the solution by water-bath heating. 2.2 Physical measurements

in 95% ethanol solution. The pH of the mixture solution was controlled in a range of 67 by adding 1 mol L1 NaOH solution. Then the ethanol solution of the two ligands was added dropwise into the LnCl36H2O [Ln = Nd, Sm, Tb] (0.5 mmol) aqueous solution under stirring. The reaction mixture was continually stirred about 10 h at room temperature, and then deposited overnight. Subsequently, the precipitates were obtained by filtration, washed with 95% ethanol and dried in a far infrared dryer. The powders finally were stored in a silica-gel desiccator for later characterization. The mother liquors were left to stand at room temperature for about two weeks and the resulting crystals were selected out and washed with distilled water. The transparent crystals produced were suitable for X-ray diffraction analysis. Elemental analyses for C66H34Cl6F6N4O12Nd2 (1) (%): Calcd., C 46.90, H 2.03, N 3.31, Nd 17.07; Found, C 47.22, H 2.09, N 3.31, Nd 16.92. For C66H34Cl12N4O12Sm2 (2) (%): Calcd., C 44.01, H 1.90, N 3.11, Sm 16.70; Found, C 43.83, H 1.91, N 3.06, Sm 16.69. For C66H34Cl12N4O12Tb2 (3) (%): Calcd., C 43.60, H 1.88, N 3.08, Tb 17.48; Found, C 43.88, H 1.87, N 3.15, Tb 17.73. For C66H32Cl6F12N4O14Sm2 (4) (%): Calcd., C 42.93, H 1.75, N 3.03, Sm 16.29; Found, C 43.79, H 1.65, N 3.17, Sm 16.51. 2.4 Data collection and structure refinements The single crystal X-ray diffraction data of complexes 14 were obtained on a Saturn724+ diffractometer with graphite-monochromated Mo-K radiation ( = 0.071073 nm) at 93(2) K. The structures were solved by direct methods using the SHELXS-97 program[19] and refined by full-matrix least-squares on F2 using the SHELXL-97 program[20]. Table 1 summarizes the crystallographic data and details of the structure refinements for 14. In addition, non-hydrogen atom coordinates and anisotropic temperature factors were obtained using the SHELXL-97 program by full-matrix least squares amendment and hydrogen atoms were placed by the theoretical calculation. CCDC 775372 (1), 775378 (2), 775376 (3), 775375 (4) are the numbers of the four complexes, which contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif.

The contents of C, H and N were determined using a Vario-EL III element analyzer and the metal content was assayed using an EDTA titration method. IR spectra were recorded on a BRUKER TENSOR27 spectrometer in the range of 4000400 cm1 using the conventional KBr discs technique at room temperature. Ultraviolet spectra were depicted in a SHIMADZU 2501 spectrometer. The fluorescent spectra were measured on an F-4500 Hitachi spectrophotometer in the solid state at room temperature. TG/DSCFTIR coupled measurements for the title complexes were conducted using a NETZSCH STA 449 F3 instrument coupled with a BRUKER TENSOR27 Fourier Transform Infrared Spectrometer. About 8 mg samples were heated in open Al2O3 crucibles with Al2O3 crucible as a reference and the furnace temperature was programmed to rise from 303.15 to 1250 K linearly at the rates of 5, 7, 10, and 15 K min1 respectively with simulated air atmosphere as the carrier gas (protective gas and purge gas 2 are nitrogen, purge gas 1 is oxygen and their flow rates are 20, 40 and 15 mL min1). The NETZSCH STA 449 F3 instrument was linked to the heated gas cell of the FTIR Instrument by means of a heated transfer line and the temperatures of the cell and the transfer line were kept at 473.15 K. 2.3 Preparation of the complexes

3
3.1

Results and discussion

Infrared spectra

2-Chloro-4-fluorobenzoic acid (2-Cl-4-FHBA), 2,5-dichlorobenzoic acid (2,5-DClHBA) or 2-chloro-4,5-difluorobenzoaic acid (2-Cl-4,5-DFHBA) (1.5 mmol) and 1,10phenanthroline (phen) (0.5 mmol) were dissolved together

To verify the formation of the complexes, evidence was obtained by comparing the infrared spectra of the ligands and complexes in the wavenumber region 4000400 cm1. Table 2 presents the most characteristic bands and their corresponding assignments. When the coordination reaction takes place, the strong bands at 16951714 cm1 due to the

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Table 1 Crystal data and structure refinement for 14 Item Empirical formula Formula weight Temperature (K) Wavelength (nm) Crystal system Space group a (nm) b (nm) c (nm) () () () Volume (nm3) Z, calc (mg m3) Absorption coefficient (mm1) F(000) Crystal size (mm) Theta range for data collection () Limiting indices Reflections collected/unique Completeness to theta = 27.49 Max. and min. transmission Data / restraints / parameters Goodness-of-fit on F2 Final R indices [I > 2(I)] R indices (all data) 1 C66H34Cl6F6N4O12Nd2 1690.15 93(2) 0.071073 Triclinic, p 1.0699(2) 1.2405(3) 2.5471(6) 80.266(8) 83.274(7) 71.066(7) 3.1448(12) 2, 1.785 1.973 1660 0.19 0.14 0.07 3.01 to 27.48 13h13, 16k16, 31l33 31776 / 14253 [R(int) = 0.0431] 98.8 % 0.8742 and 0.7056 14253 / 2 / 865 1.002 a) R1 = 0.0427, b) wR2 = 0.0869 R1 = 0.0640, wR2 = 0.0951 2 C66H34Cl12N4O12Sm2 1801.07 93(2) 0.071073 Triclinic, p 1.1282(2) 1.3246(3) 1.3351(3) 109.0610(10) 108.6400(10) 103.684(2) 1.6523(6) 1, 1.810 2.311 882 0.37 0.37 0.37 3.01 to 27.48 14h14, 16k17, 17l17 15562 / 7476 [R(int) = 0.0270 ] 98.8 % 0.4843 and 0.4843 7476 / 0 / 433 1.002 R1 = 0.0265, wR2 = 0.0541 R1 = 0.0304, wR2 = 0.0558 3 C66H34Cl12N4O12Tb2 1818.2 93(2) 0.071073 Triclinic, p 1.1358(2) 1.3263(3) 1.3272(3) 108.618(10) 108.9640(10) 104.2450(2) 1.6497(5) 1, 1.830 2.678 888 0.30 0.27 0.13 3.02 to 27.49 14h14, 17k16, 16l17 16694 / 7472 [R(int) = 0.0270 ] 98.7% 0.7171 and 0.5004 7472 / 0 / 433 0.999 R1 = 0.0253, wR2 = 0.0528 R1 = 0.0291, wR2 = 0.0543 4 C66H32Cl6F12N4O14Sm2 1846.36 93(2) 0.071073 Triclinic p 1.08195(19) 1.1575(2) (2) 1.4292(3) 1104.322(3) 103.3700(10) 102.443(2) 1.6150(5) 1, 1.898 2.155 902 0.25 0.22 0.17 3.07 to 27.49 13h14, 15k14, 18l18 14937 / 7302 [R(int) = 0.0236] 98.5 % 0.7149 and 0.6149 7302 / 0 / 477 0.998 R1 = 0.0234, wR2 = 0.0518 R1 = 0.0279, wR2 = 0.0535

a) R1 = ||Fo|-|Fc||/|Fo| b) wR2= [{w(Fo2-Fc2)2}]1/2/{w( Fo2)2}]1/2.

Table 2

Important IR absorption bands for the ligands and complexes (cm1) Compounds phen 2,5-DClHBA 2-Cl-4-FHBA 2-Cl-4,5-DFHBA 1 2 3 4 C=N 1561 1519 1519 1519 1519 C=O 1704 1695 1714 as(COO) 1619 1621 1619 1631 s(COO) 1402 1411 1412 1426 854 843 844 846 845 C-H 738 729 730 730 731 Ln-O 417 416 426 417

C=O (COOH ) in the three free acid ligands are replaced by the two characteristic bands of as(COO) and s(COO) around 16191631 and 14021426 cm1, indicating that the oxygen atoms of the carboxylate groups have formed coordinative bonds with Ln3+ ions [21]. Meanwhile, the appearance of absorption bands at 416426 cm1 attributed to the Ln-O also suggests that the oxygen atoms from the carboxylate group are coordinated to Ln3+ ions. The bands of C=N (1561 cm1), C-H (854 and 738 cm1) in the spectrum of phen ligand are

observed to shift to lower wavenumbers in the spectra of the complexes, suggesting the coordination of both nitrogen atoms of the neutral ligand to Ln3+ ions [22]. 3.2 Ultraviolet spectra

The ligands and complexes were recorded in DMSO (dimethyl sulfoxide) solution by UV spectra with DMSO as a reference, separately. The spectrum data are listed in Table

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3. The maximum absorption wavelengths of the three free acid ligands are 256.0256.2 nm and the respective absorbency is 0.02, 0.18 and 0.15. The main absorption peaks of the complexes are 264.6265.3 nm, which may lead to the conclusion that the free acid ligands are coordinated to the metal ion forming a -conjugated system [23]. Moreover, compared with the complexes, the maximum absorption peak of phen at 265.0 nm is similar to that of the complexes, indicating that the formation of the coordination bonds of Ln-N has no significant influence on the UV absorption of the phen [24]. However, the absorbency is enhanced from 0.31 to 0.93, 1.3, 0.97 or 0.81 for complexes 14, respectively, suggesting a chelating complex is formed. 3.3 X-Ray diffraction studies

slow evaporation. X-ray single crystal diffraction results show that the four complexes crystallize in the same crystal system triclinic space group P and they are all binuclear molecules with a crystallographic inversion center. The selected bond lengths for 14 are listed in Tables 46, respectively.
Table 3 UV absorption of the ligands and complexes Compounds phen 2-Cl-4-FHBA 2,5-DClHBA 2-Cl-4,5-DFHBA 1 2 3 4 max (nm) 265.0 256.0 256.0 256.2 265.3 264.6 265.0 265.2 Amax 0.31 0.02 0.18 0.15 0.93 1.30 0.97 0.81

Light purple crystal of 1 and colorless crystals of 24 were obtained from the mother liquors at room temperature by
Table 4 Selected bond distances (nm) and angles () for 1 1 Nd(1)-O(5)#1a) Nd(1)-O(3) Nd(1)-O(5) Nd(1')-O(6')#2b) Nd(1')-O(2')#2 Nd(1')-O(3') O(5)#1-Nd(1)-O(2)#1 O(5)#1-Nd(1)-O(1) O(2)#1-Nd(1)-O(1) O(5)#1-Nd(1)-O(3) O(2)#1-Nd(1)-O(3) O(1)-Nd(1)-O(3) O(5)#1-Nd(1)-O(6) O(2)#1-Nd(1)-O(6) O(1)-Nd(1)-O(6) O(3)-Nd(1)-O(6) O(5)#1-Nd(1)-O(4) O(4)-Nd(1)-N(2) O(6')#2-Nd(1')-O(1') O(6')#2-Nd(1')-O(3') O(6')#2-Nd(1')-O(4') O(3')-Nd(1')-O(4') O(2')#2-Nd(1')-O(5') O(6')#2-Nd(1')-N(1') O(3')-Nd(1')-N(1') O(6')#2-Nd(1')-O(6') O(3')-Nd(1')-O(6') N(1')-Nd(1')-O(6') O(2')#2-Nd(1')-N(2') O(5')-Nd(1')-N(2') 0.2403(3) 0.2460(3) 0.2600(3) 0.2399(3) 0.2442(3) 0.2494(3) 73.42(10) 77.29(10) 136.87(9) 84.05(10) 77.22(10) 130.30(10) 124.08(9) 83.90(10) 87.08(10) 139.72(10) 78.27(10) 98.35(10) 75.11(10) 77.23(10) 89.33(10) 52.21(9) 92.14(10) 144.48(10) 73.12(10) 72.53(10) 136.30(10) 118.11(10) 77.76(10) 66.28(10) Nd(1)-O(2)#1 Nd(1)-O(6) Nd(1)-N(1) Nd(1')-O(5') Nd(1')-O(6') Nd(1')-N(2') O(2)#1-Nd(1)-O(4) O(1)-Nd(1)-O(4) O(3)-Nd(1)-O(4) O(6)-Nd(1)-O(4) O(5)#1-Nd(1)-O(5) O(2)#1-Nd(1)-O(5) O(1)-Nd(1)-O(5) O(3)-Nd(1)-O(5) O(6)-Nd(1)-O(5) O(4)-Nd(1)-O(5) O(5)#1-Nd(1)-N(1) O(5)-Nd(1)-N(2) O(6')#2-Nd(1')-O(2')#2 O(1')-Nd(1')-O(3') O(1')-Nd(1')-O(4') O(6')#2-Nd(1')-O(5') O(3')-Nd(1')-O(5') O(1')-Nd(1')-N(1') O(4')-Nd(1')-N(1') O(1')-Nd(1')-O(6') O(4')-Nd(1')-O(6') O(6')#2-Nd(1')-N(2') O(3')-Nd(1')-N(2') N(1')-Nd(1')-N(2')

0.2425(3) 0.2542(3) 0.2635(3) 0.2544(3) 0.2638(3) 0.2670(4) 123.87(10) 78.87(10) 52.20(9) 150.35(9) 73.63(11) 73.08(9) 68.68(9) 146.81(9) 50.80(9) 140.74(9) 143.33(10) 120.42(10) 74.64(10) 74.81(10) 126.94(9) 122.54(10) 139.85(9) 78.58(10) 87.74(11) 67.49(9) 153.71(9) 151.18(10) 114.71(10) 62.30(10)

Nd(1)-O(1) Nd(1)-O(4) Nd(1)-N(2) Nd(1')-O(1') Nd(1')-N(1') Nd(1')-O(4') O(2)#1-Nd(1)-N(1) O(1)-Nd(1)-N(1) O(3)-Nd(1)-N(1) O(6)-Nd(1)-N(1) O(4)-Nd(1)-N(1) O(5)-Nd(1)-N(1) O(5)#1-Nd(1)-N(2) O(2)#1-Nd(1)-N(2) O(1)-Nd(1)-N(2) O(3)-Nd(1)-N(2) O(6)-Nd(1)-N(2) N(1)-Nd(1)-N(2) O(1')-Nd(1')-O(2')#2 O(2')#2-Nd(1')-O(3') O(2')#2-Nd(1')-O(4') O(1')-Nd(1')-O(5') O(4')-Nd(1')-O(5') O(2')#2-Nd(1')-N(1') O(5')-Nd(1')-N(1') O(2')#2-Nd(1')-O(6') O(5')-Nd(1')-O(6') O(1')-Nd(1')-N(2') O(4')-Nd(1')-N(2') O(6')-Nd(1')-N(2')

0.2433(3) 0.2551(3) 0.2657(3) 0.2418(3) 0.2595(3) 0.2509(3) 140.99(10) 78.03(10) 91.71(10) 81.01(10) 70.65(11) 120.82(10) 144.38(10) 79.85(10) 137.44(10) 67.18(11) 74.70(10) 61.53(10) 135.43(10) 127.92(10) 84.46(10) 77.59(10) 145.86(10) 140.05(10) 73.27(10) 72.65(10) 50.38(9) 132.32(10) 79.84(10) 106.90(10)

Symmetry transformations used to generate equivalent atoms: a) #1 x+2, y, z+2, b) #2 x+1, y+2.

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Table 5

Selected bond distances (nm) and angles () for 2 and 3 2 0.23786(16) 0.24204(18) 0.2582(2) 75.33(6) 83.81(6) 76.38(6) 53.59(6) 78.29(6) 145.04(6) 92.06(6) 143.97(6) 70.65(6) 63.22(7) 68.99(6) 50.89(5) 0.23462(17) 0.23906(18) 0.2556(2) 75.78(6) 83.21(6) 76.41(6) 54.01(6) 78.53(6) 144.27(6) 93.41(6) 144.16(6) 70.88(6) 63.91(7) 68.79(5) 51.18(5) Sm(1)-O(2)#1 Sm(1)-O(5) Sm(1)-N(1) O(3)#1-Sm(1)-O(1) O(2)#1-Sm(1)-O(6) O(2)#1-Sm(1)-O(5) O(3)#1-Sm(1)-O(4) O(6)-Sm(1)-O(4) O(2)#1-Sm(1)-N(2) O(5)-Sm(1)-N(2) O(2)#1-Sm(1)-N(1) O(5)-Sm(1)-N(1) O(3)#1-Sm(1)-O(3) O(6)-Sm(1)-O(3) N(2)-Sm(1)-O(3) 3 Tb(1)-O(2)#1 Tb(1)-O(5) Tb(1)-N(1) O(3)#1-Tb(1)-O(1) O(2)#1-Tb(1)-O(6) O(2)#1-Tb(1)-O(5) O(3)#1-Tb(1)-O(4) O(6)-Tb(1)-O(4) O(2)#1-Tb(1)-N(2) O(5)-Tb(1)-N(2) O(2)#1-Tb(1)-N(1) O(5)-Tb(1)-N(1) O(3)#1-Tb(1)-O(3) O(6)-Tb(1)-O(3) N(2)-Tb(1)-O(3) 0.23840(17) 0.24774(18) 0.2609(2) 74.66(6) 82.38(6) 129.48(6) 122.67(5) 150.10(6) 138.64(6) 73.40(6) 76.42(6) 105.83(6) 72.31(6) 147.38(5) 120.23(6) 0.23549(17) 0.24575(17) 0.2580(2) 74.66(6) 81.91(6) 129.88(6) 122.85(6) 150.00(6) 139.14(6) 73.05(6) 76.39(6) 105.54(6) 72.14(6) 146.35(6) 119.98(6) Sm(1)-O(1) Sm(1)-O(4) Sm(1)-O(3) O(2)#1-Sm(1)-O(1) O(1)-Sm(1)-O(6) O(1)-Sm(1)-O(5) O(2)#1-Sm(1)-O(4) O(5)-Sm(1)-O(4) O(1)-Sm(1)-N(2) O(4)-Sm(1)-N(2) O(1)-Sm(1)-N(1) O(4)-Sm(1)-N(1) O(2)#1-Sm(1)-O(3) O(5)-Sm(1)-O(3) N(1)-Sm(1)-O(3) Tb(1)-O(1) Tb(1)-O(4) Tb(1)-O(3) O(2)#1-Tb(1)-O(1) O(1)-Tb(1)-O(6) O(1)-Tb(1)-O(5) O(2)#1-Tb(1)-O(4) O(5)-Tb(1)-O(4) O(1)-Tb(1)-N(2) O(4)-Tb(1)-N(2) O(1)-Tb(1)-N(1) O(4)-Tb(1)-N(1) O(2)#1-Tb(1)-O(3) O(5)-Tb(1)-O(3) N(1)-Tb(1)-O(3) 0.23975(17) 0.24982(17) 0.26162(17) 135.07(6) 126.11(6) 73.33(6) 90.84(6) 139.66(6) 80.14(6) 73.97(6) 141.12(6) 79.44(6) 70.48(6) 135.89(5) 117.81(6) 0.23667(17) 0.24576(18) 0.26144(16) 134.99(6) 126.66(6) 73.64(6) 90.07(6) 140.01(6) 79.28(6) 74.00(6) 140.93(6) 79.15(6) 70.25(6) 135.89(5) 118.11(6)

Sm(1)-O(3)#1c) Sm(1)-O(6) Sm(1)-N(2) O(3)#1-Sm(1)-O(2)#1c) O(3)#1-Sm(1)-O(6) O(3)#1-Sm(1)-O(5) O(6)-Sm(1)-O(5) O(1)-Sm(1)-O(4) O(3)#1-Sm(1)-N(2) O(6)-Sm(1)-N(2) O(3)#1-Sm(1)-N(1) O(6)-Sm(1)-N(1) N(2)-Sm(1)-N(1) O(1)-Sm(1)-O(3) O(4)-Sm(1)-O(3) Tb(1)-O(3)#1c) Tb(1)-O(6) Tb(1)-N(2) O(3)#1-Tb(1)-O(2)#1c) O(3)#1-Tb(1)-O(6) O(3)#1-Tb(1)-O(5) O(6)-Tb(1)-O(5) O(1)-Tb(1)-O(4) O(3)#1-Tb(1)-N(2) O(6)-Tb(1)-N(2) O(3)#1-Tb(1)-N(1) O(6)-Tb(1)-N(1) N(2)-Tb(1)-N(1) O(1)-Tb(1)-O(3) O(4)-Tb(1)-O(3)

Symmetry transformations used to generate equivalent atoms: c) #1 x+1, y+1, z+1. Table 6 Selected bond distances (nm) and angles () for 4 Sm(1)-O(3)#1c) Sm(1)-O(3) Sm(1)-O(2)#1 O(3)#1-Sm(1)-O(5) O(3)#1-Sm(1)-O(2)#1 O(3)#1-Sm(1)-O(7) O(2)#1-Sm(1)-O(7) O(1)-Sm(1)-O(4) O(3)#1-Sm(1)-N(2) O(1)-Sm(1)-N(2) O(4)-Sm(1)-N(2) O(1)-Sm(1)-N(1) O(4)-Sm(1)-N(1) O(5)-Sm(1)-O(3) O(7)-Sm(1)-O(3) N(1)-Sm(1)-O(3) 0.23612(15) 0.27337(16) 0.24131(15) 78.28(5) 76.88(5) 88.45(6) 140.34(6) 84.56(5) 147.25(6) 138.25(6) 74.46(6) 75.52(5) 64.68(5) 132.51(5) 143.81(6) 106.36(5) Sm(1)-O(4) Sm(1)-O(1) Sm(1)-N(1) O(3)#1-Sm(1)-O(1) O(5)-Sm(1)-O(2)#1 O(5)-Sm(1)-O(7) O(3)#1-Sm(1)-O(4) O(2)#1-Sm(1)-O(4) O(3)#1-Sm(1)-N(2) O(2)#1-Sm(1)-N(2) O(3)#1-Sm(1)-N(1) O(2)#1-Sm(1)-N(1) N(2)-Sm(1)-N(1) O(1)-Sm(1)-O(3) O(4)-Sm(1)-O(3) O(3)#1-Sm(1)-C(14) 4 0.24999(16) 0.23962(16) 0.26419(18) 74.24(5) 71.45(5) 69.54(6) 122.24(5) 79.83(5) 147.25(6) 79.32(6) 147.89(6) 133.18(6) 62.96(6) 69.72(5) 49.53(5) 97.85(6) Sm(1)-O(5) Sm(1)-N(2) Sm(1)-O(7) O(5)-Sm(1)-O(1) O(1)-Sm(1)-O(2)#1 O(1)-Sm(1)-O(7) O(5)-Sm(1)-O(4) O(7)-Sm(1)-O(4) O(5)-Sm(1)-N(2) O(7)-Sm(1)-N(2) O(5)-Sm(1)-N(1) O(7)-Sm(1)-N(1) O(3)#1-Sm(1)-O(3) O(2)#1-Sm(1)-O(3) N(2)-Sm(1)-O(3) 0.23877(16) 0.25710(19) 0.24792(18) 135.70(6) 132.36(5) 75.59(6) 139.74(5) 137.22(6) 72.99(6) 95.84(6) 117.91(5) 73.74(6) 72.72(6) 65.91(5) 116.82(5)

Symmetry transformations used to generate equivalent atoms: c) #1 x+1, y+1, z+1.

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Structure description of 1 For complex 1, in the asymmetric part, two different Nd(2-Cl-4-FBA)3 phen units are combined through invention with the corresponding units of the closest asymmetric species respectively, and thus there are two types of binu-

clear molecules in its crystal, as shown in Figure 1(a) and (b). The two Nd(III) ions in each molecular structure are joined together by four 2-Cl-4-FBA groups, two of which adopt a bridging bidentate mode and the other two a bridging-chelating tridentate mode. In addition, each Nd(III) ion-

Figure 1 clarity).

Molecular structure and atom labeling scheme for complex 1 with thermal ellipsoids at 50% probability (All hydrogen atoms are omitted for

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is also chelated by one 2-Cl-4-FBA group and one phen molecule, giving the coordination number of nine. However, there are two different coordination polyhedrons for Nd(III) ions with a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation (See Figure 2). In Figure 2(a), atom O5 locates at the capped position, atoms O1, O6, O2A and O5A form the topside plane of the square antiprism and the underside plane is formed by atoms N1, N2, O3 and O4. In Figure 2(b), atoms N2A, O3A and O6A locate at the capped positions, atoms O2, O4A and O6 are composed of the topside face of the tricapped triangular prism and atoms O5, N1A and O1A comprise the underside face. The Nd-Nd distances are 0.40070(9) and 0.40636(9) nm in Figure 1(a) and (b). The average lengths of Nd-O are 0.2488 nm and 0.2492 nm and Nd-N lengths

are 0.2641 nm and 0.2632 nm, respectively. Structure description of 2 and 3 For complexes 2 and 3, the molecular structures and the detailed coordination spheres around the center ions Sm3+ and Tb3+ are shown in Figures 3 and 4, respectively. These two complexes are isostructural with each other observed from Figures 3 and 4. Here, complex 2 is chosen as a representative for detailed discussion. As shown in Figure 3(a), two Sm3+ ions, six 2,5-DClBA groups and two phen molecules are contained in a centrosymmetric unit. The two center Sm3+ ions of the molecular structure are connected together by four 2,5-DClBA groups, with two of them in a bridging bidentate mode and the other two a bridging-chelating tridentate mode, which is similar to complex 1.

Figure 2

Coordination geometries of the Nd3+ ions in the two types of complex 1.

Figure 3 (a) Molecular structure of complex 2. All hydrogen atoms are omitted for clarity, and thermal ellipsoids are drawn at the 50% probability level; (b) coordination geometry of the Sm3+ ion.

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Figure 4 (a) Molecular structure of complex 3. All hydrogen atoms are omitted for clarity, and thermal ellipsoids are drawn at the 50% probability level. (b) Coordination geometry of the Tb3+ ion.

The distance between the two Sm3+ ions is 0.40354(9) nm. In addition, each Sm3+ ion is further chelated by one 2,5-DClBA group and one phen molecule, yielding a nine-coordinated distorted monocapped square antiprismatic conformation (Figure 3(b)), in which atom O3 locates at the capped position, atoms O1, O4, O2A and O3A form the topside plane of the square antiprism and the underside plane is formed by atoms N1, N2, O5 and O6. The distances of Sm-O are from 0.23786(16) nm to 0.26162(17) nm, with an average value of 0.24532(17) nm. The average bond length of SmO from the chelating mode of the carboxylate groups (2.5031 nm) is longer than that of SmO (0.23867 nm) from the bridging mode carboxylate groups, Therefore, the carboxylate groups may not be released simultaneously, but partially decomposed. Which explains the result that part of the carboxyl groups decomposed in the first stage of the thermal decomposition. The lengths of Sm-N bonds are 0.2582(2) and 0.2609(2) nm with a mean bond length of 0.2596 (2) nm. In complexes 13, the average bond length of LnO formed by the chelating mode of the carboxylate groups is longer than that of LnO from the bridging mode, which may be due to the instability of the four-membered ring or caused by lower electrostatic interaction as negative charge of the carboxylate is delocalized over two oxygen atoms [25].

Structure description of 4 For complex 4, the molecular structure and the detailed coordination sphere around the Sm3+ ion are shown in Figure 5. As shown in Figure 5(a), two Sm3+ ions, six 2-Cl4,5-DFBA, two phen and two H2O are contained in a centrosymmetric unit. In the molecular structure, carboxyl groups have three kinds of coordination modes, unidentate, bridging bidentate and bridging-chelating tridentate. It is also observed that each Sm3+ ion is coordinated by seven oxygen atoms of carboxyl groups except one from a bonding water and two nitrogen atoms of a phen, yielding a distorted monocapped square antiprismatic conformation, in which atom O3 locates at the top of the cap, atoms O4, O3A, O2A and O1 form one square face and the other face is formed by atoms N1, N2, O5 and O7 (See Figure 5(b)). The distances of SmO are from 0.23612(15) to 0.27337(16) nm, with an average value of 0.24672 nm. The lengths of Sm-N bonds are 0.25710(19) and 0.26419(18) nm with a mean bond length of 0.26065 nm. By comparing the two mean bond distances, we know that the bond energy of LnO is stronger than that of the Ln-N bond in all complexes, so the neutral ligand phen should be lost firstly, which can be demonstrated by the thermal decomposition process. In a word, when compared to the structures of the four complexes, they have both similarities and differences. They have similar coordination modes and different coordination polyhedron, which may be related with the compo-

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Figure 5 (a) Molecular structure of complex 4. All hydrogen atoms are omitted for clarity, and thermal ellipsoids are drawn at the 50% probability level; (b) coordination geometry of the Sm3+ ion.

sition and structures of the lanthanide complexes. 3.4 Fluorescence spectra The terbium complexes have good stability and the emission wavelength do not change with the ligands. In addition, the complexes emit high luminous intensity and show good monochromaticity on UV light. Here, the excitation wavelengths of complex 3 in the solid state were performed in the range of 200400 nm and it exhibits green luminescence under the radiation of UV light. The fluorescent spectrum was observed in the range of 400700 nm by selective excitation wavelength at 330 nm, as shown in Figure 6. For complex 3, there are four main emission peaks in the luminescence spectrum at about 490, 545, 585 and 619 nm, which are assigned to the 5D4-7F6, 5 D4-7F5, 5D4-7F4 and 5D4-7F3 transitions of the Tb3+ ion, respectively. The strongest emission is at 545 nm due to the 5 D4-7F5 transition which is the preferred transition in terbiumcontaining complexes [26]. 3.5 Thermal decomposition processes of the complexes

Figure 6 Excitation spectra ( = 545 nm) and luminescence spectra ( = 330 nm) of complex 3.

The thermal analysis curves of 14 at a heating rate of 10 K min1 under a dynamic simulated air atmosphere (flow rate 75 mL min1) are shown in Figure 7. The thermal analytical

data for the complexes are listed in Table 7. Seen from the DTG curves, the thermal decomposition processes of the four complexes all present two main successive mass loss stages. The first one is connected with the degradation of the ligands and the second one is related with the degradation and oxidation process. From the profiles of the TG-DTG curves and the thermal analytical data of 13, we draw a conclusion that they have similar thermal decomposition processes. Here, we take

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Figure 7 plex 4.

The curves of TG-DTG, and heatflow of complexes 14 at the heating rate of 10 K min1. (a) Complex 1; (b) complex 2; (c) complex 3; (d) com-

Table 7

Thermal decomposition data for 14 Step I 1 II Temperature range (K) 523.15-754.15 754.15-1231.15 DSC (Tp, K) 559.65 728.25 803.15 555.15 715.15 800.15 552.15 565.15 728.15 808.15 526.05 555.35 710.15 798.55 DTG (Tp, K) 719.15 799.15 Mass loss rate (%) Found 65.57 13.96 79.82 I 2 II 529.15-746. 15 746.15-1261.15 700.15 794.15
a)

Complexes

Calcd. 80.09 80.64 a) 79.30 a) 81.11 a)

a)

Probable expelled groups 2phen+ x(2-Cl-4-FBA) (6-x)( 2-Cl-4-FBA)-3O 2phen+ x(2,5-DClBA) (6-x)(2,5-DClBA)-3O

60.66 18.44 79.35 a)

I 3 II

533.15-759.15 759.15-1218.15

708.15 805.15

59.53 19.99 79.44 a)

2phen+ x(2,5-DClBA) (6-x)(2,5-DClBA)-3.5O 2H2O+2phen+x(2-Cl-4,5-DFBA) (6-x)(2-Cl-4,5-DFBA)-3O

I 4 II

507.15-744.15 744.15-1159.15

687.15 794.15

63.69 17.25 81.38 a)

Tp is the peak temperature of DTG or DSC. a) is the total loss rate.

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complex 1 as an example to discuss their detailed thermal decomposition processes. For complex 1, the first stage mass loss is 65.57% between 523.15 and 754.15 K, which corresponds to the loss of two phen molecules and partial 2-Cl-4-FBA ligands. This process is accompanied by one endothermic and one exothermic peak at about 559.65 and 728.25 K, indicating the release of phen is endothermic effect, while the release of 2-Cl-4-FBA ligands is exothermic effect. The second stage takes place at 754.15 K and continues to 1231.15 K with a loss of 13.96%, corresponding to the loss of the rest groups. On the DSC curve, strong exothermic effect is observed at about 803.15 K, corresponding to the degradation and oxidation of the rest 2-Cl-4-FBA ligands. The final residue is verified by IR spectra and the result indicates that the spectrum has similar characteristic absorptions compared with the standard sample spectrum of Nd2O3. Therefore, Up to 1231.15 K, complex 1 is completely degraded into Nd2O3 with a total loss of 79.82% (theoretical loss is 80.09%). For complexes 2 and 3, the first stage corresponds to the loss of two phen molecules and partial 2,5-DClBA ligands. There are four peaks on the DSC curve for complex 3: the first two endothermic peaks corresponding to the loss of two phen molecules and the latter two exothermic peaks corresponding to the loss of 2,5-DClBA ligands. Based on the above analysis, the thermal decomposition of 13 can be described as the following process: [Nd(2-Cl-4-FBA)3phen]2 [Nd(2-Cl-4-FBA)3-x]2 Nd 2O3 [Sm(2,5-DClBA)3phen]2 [Sm2(2,5-DClBA)3-x]2 Sm2O3 [Tb(2,5-DClBA)3phen]2 [Tb2(2,5-DClBA)3-x]2 1/2Tb4O7. For complex 4, the first stage mass loss is 63.69% between 507.15 and 687.15 K, which corresponds to the loss of two water, two phen molecules and partial 2-Cl-4,5-DFBA ligands. This process is accompanied by two endothermic peaks and one exothermic peak. The first two successive endothermic peaks at about 526.05 and 555.35 K correspond to the loss of two water and two phen molecules, respectively. The exothermic peak appears between 617.15 and 732.15 K, representing the release of partial 2-Cl-4,5-DFBA ligands. The second stage takes place at 744.15 K and continues to 1159.15 K with a loss of 17.25%, corresponding to the loss of the rest groups. On the DSC curve the second strong exothermic effect is observed at about 798.55 K, corresponding to the degradation and oxidation of the rest 2-Cl-4,5-DFBA ligands. The percentage value (18.62%) of the final residue is consistent with the theoretical percentage 18.89% of the oxide Sm2O3. The final residue is also verified by IR spectra and the spectrum has similar characteristic absorptions compared with the standard sample spectrum of Sm2O3, that is, up to 1159.15

K, complex 4 is completely degraded into Sm2O3 with a total loss of 81.38% (theoretical loss is 81.11%). Based on the above analysis, the thermal decomposition of complex 4 can be presented as the following process: [Sm(2-Cl-4,5-DFBA)3(phen)(H2O)]2 [Sm(2-Cl-4,5-DFBA)3-x]2 Sm 2O3. We draw the conclusion from the above analyses that the four complexes all have good thermostability due to the higher decomposed temperatures until 507 K, which results from the stable structures of the four complexes. The first stage mass loss is also accompanied by part of the halogen benzoate and the final obtained solid residues are corresponding metal oxides: Ln2O3 (for Nd and Sm) and Tb4O7. In addition, Ln-N bonds of the complexes break firstly (except the bonds of SmO in complex 4, in which the oxygen atom is from the bonding water) in the TG experiments, which may be explained by the longer bond of LnN than that of LnO. 3.6 TG-FTIR spectra of gaseous products

The gaseous products from TG experiments were detected online and identified by using infrared spectra in dynamic simulated air atmosphere. The stacked plots of the FTIR spectra of the gaseous products are shown in Figure 8. It shows that the escape of gaseous products is mainly in two steps, which is consistent with the TG experiments. Figures 912 plot the typical IR spectra obtained at two temperatures for each complex, where the complex has the most gaseous products for each thermal decomposition step. In addition, the two temperatures are very close to the DTG peak temperatures for each complex. On the basis of the thermal analyses from the TG-DTG curves, we know that the complexes lost not only the two phen molecules but also the partial halogen benzoate ligands in the first step, so this step should produce most kinds of gases. From the IR spectra of the first step plotted in Figures 9-12, we observe that except the absorption bands of CO2 (2361-2307, 670 cm1), there is no other small molecular absorption, such as H2O (except complex 4), alkanes and alkenes, indicating that the aromatic rings in the two organic ligands may not be broken. This result is different from the gaseous products of the non-substituted benzoic acid complex [Ho(BA)3phen]2 [27]. Figure 9 shows the IR absorbance of the gaseous products escaping from complex 1. The following gaseous species at 722.33 K can be identified by their characteristic absorbance: CO2 (2360-2310, 669 cm1); phen (C=C, C=N 1600, 1486, C-N 1259 cm1); C7H4ClF (=CH 3088, C=C 1600, 1486, =CH 886, 774, =CH (in-plane) 1160, 1128, 1095, CCl 774, CF 1259 cm1); C7H4O2ClF (=CH 3088, C=O 1691, C=C 1600, 1486, =CH 886, 829, 774, COOH 1261, 1234, =CH 1160, 1128, 1095, CCl 774, CF 1259 cm1). The IR spectra at 709.14 and

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Figure 8 Stacked plots of the FTIR spectra of the evolved gases for complexes 14 as observed in the online TG/DSC-FTIR system at the heating rate of 10 K min1. (a) Complex 1; (b) complex 4; (c) complex 2; (d) complex 3.

Figure 9

FTIR spectra of the gaseous mixtures for complex 1 at (722.33 and 807.23) K.

715.14 K plotted in Figures 10 and 11 for the first step of complexes 2 and 3 have similar infrared signals, probably because of the similar structures due to the identical ligands. Hence, here we take the IR spectra of complex 2 as an example to analyze the gaseous species of the thermal decomposition processes for the two complexes. The main gaseous species can be identified by their characteristic absorbance: CO2 (2357-2311, 670 cm1); phen (C=C, C=N

1583, 1476, C-N 1284, =CH 784 cm1); C7H4Cl2 (=CH 3048, 3086, C=C 1583, 1476, =CH 821, =CH 1222, 1094, 1017, CCl 784, CF 1284 cm1). For the complex 4, the main gaseous species of the first step can be identified from the IR spectra at 702.72 K plotted in Figure 12: H2O (3738 cm1), CO2 (2360-2310, 669 cm1); phen (C=C, C=N 1610, 1505, C-N 1284, CH 861, 778 cm1); C7H3ClF2 (=CH 3082, C=C 1610, 1505, =CH 861, =CH 1214, 1115, 1078, CCl 778,

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13

Figure 10

FTIR spectra of the gaseous mixtures for complex 2 at (709.14 and 794.11) K.

Figure 11

FTIR spectra of the gaseous mixtures for complex 3 at (715.93 and 808.11) K.

Figure 12

FTIR spectra of the gaseous mixtures for complex 4 at (702.72 and 806.84) K.

CF 908 cm1); C7H3O2ClF2 (C=H 3082, C=O 1683, C=C 1610, 1505, =CH 861, 807, OH 908, OH 1408, =CH 1214, 1115, 1078, CCl 778, CF 908 cm1). Here, one cannot distinguish between all the evolved gases due to overlapping (similar wavelengths) in the FTIR spectra. From the above analyses, we infer that in the first thermal decomposition step of the four complexes, the neutral ligand phen was released as itself and the halogen benzoate was released as

CO2, the respective halogenated benzene and a small amount of halogen benzoic acid for complexes 1 and 4. From the IR spectra at 807.23, 794.11, 808.11 and 806.84 K plotted in Figures 912 for the four complexes respectively, three small molecular gaseous species are identified by their characteristic absorbance: CO 2 (2361-2307, 670 cm1), CO (2183, 2105 cm1) and H2O (37413591 cm1), indicating that the second thermal de-

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reactions [2931].

Conclusion

Figure 13 The relationship between E and for the first step by the NL-INT method.

In summary, we have obtained the crystal structures of the four new lanthanide complexes involving different kinds of lanthanide ions and halogen benzoic acids. The four complexes are all binuclear molecules and all Ln3+ ions in the complexes are nine-coordinated distorted monocapped square antiprismatic except that Nd3+ ion in complex 1 has the other coordination polyhedron, a distorted tricapped triangular prism conformation in its two similar molecule structures. The thermal behavior and the gaseous products of thermal decomposition processes of the complexes were determined by TG/DSC-FTIR technique. The two organic ligands may be released as phen, halogenated benzene, a small amount of halogen benzoic acid as well as CO2, CO and H2O. The values of E of each decomposition step for complexes 14 vary with apparently, indicating the complexity of the two thermal decomposition steps for each complex.
We thank the National Natural Science Foundation of China (21073053, 21073052 and 20773034) and the Natural Science Foundation of Hebei Province (B2012205022). 1 Li X, Shi Q, Sun DF, Bi WH, Cao R. Synthesis and characterization of a series of lanthanide complexes constructed from orotic acid. Eur J Inorg Chem, 2004(13): 27472753 Tian L, Ren N, Zhang JJ, Liu HM, Bai JH, Ye HM, Sun SJ. Synthesis, crystal structure, luminescence and thermal decomposition kinetics of Eu(III) complex with 2,4-dichlorobenzoic acid and 2, 20-bipyridine. Inorg Chim Acta, 2009, 362: 33883394 Ye HM, Ren N, Zhang JJ, Sun SJ, Wang JF. Crystal structures, luminescent and thermal properties of a new series of lanthanide complexes with 4-ethylbenzoic acid. New J Chem, 2010, 34: 533540 Li X, Li YQ, Wu XS. 1-D and 2-D lanthanide coordination polymers constructed from 4-sulfobenzoate and 1,10-phenanthroline. Inorg Chem commum, 2008, 11: 774778 Bettencourt-Das AD. Isophthalato-based 2D coordination polymers of Eu(III), Gd(III), and Tb(III): Enhancement of the terbium-centered luminescence through thiophene derivatization. Inorg Chem, 2005, 44(8): 27342741 Wan YH, Jin LP, Wang KZ, Zhang LP, Zheng XJ, Lu SZ. Hydrothermal synthesis and structural studies of novel 2-D lanthanide coordination polymers with phthalic acid. New J Chem, 2002, 26(11): 15901596 Wang CG, Xing YH, Li ZP, Li J, Zeng XQ, Ge MF, Niu SY. A series of three-dimensional lanthanide-rigid-flexible frameworks: Synthesis, structure, and luminescent properties of coordination polymers with 2,5-pyridine dicarboxylic acid and adipic acid. Crys Growth De, 2009, 9(3): 15251530 Huang CH. Coordination Chemistry of Rare Earths. Bingjing: Science Press, 1997. 378 Gao C, Cui K, She JB, Hou CQ, Guo HY, Zhao W, Wei W, Peng B. Optical properties of a novel neodymium pentafluoropropionate binuclear complex. Inorg Chim Acta, 2009, 362: 20012005 Yang SP, Yang H, Yu XB, Wang ZM. Synthesis, structure and fluorescence of Eu2(NAP)6(PHEN)2 (NAPH = -naphthoic acid; PHEN = 1,10-phenanthroline). J Mol Struct, 2003, 659: 97102

2 Figure 14 The relationship between E and for the second step by the NL-INT method. 3

compositions are oxidative decomposition process of the rest halogen benzoate ligands. The halogen atoms contained in ligands may escape in the form of Cl2 or F2, which unfortunately cannot be detected by means of FTIR analysis because symmetrical diatomic molecules are IR inactive. 3.7 Kinetics of the decomposition steps for 14

As we know, the non-isothermal multiple scan method has been widely recognized in dealing with the thermal analysis data, in which the kinetic model function is not involved and the reliable value of the activation energy E can be obtained. Therefore, here the integral isoconversional non-linear method (NL-INT method) [28] is used to calculate the activation energy E of the two decomposition steps for each complex. Figures 13 and 14 show the relationships of E varying with for the two steps. However, from the two figures, we observe that the values of E for the four complexes vary with apparently, suggesting that the two thermal decomposition steps for each complex are complex

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