系列Sm3+配合物的合成、结构及光物理性能

doi:10.7503/cjcu20140302

摘要/Abstract

摘要：

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、劈裂和加宽的原因.

关键词: Sm3+配合物, 晶体结构, 发光性能

Abstract:

Four new Sm³⁺ coordination complexes, {[SmZn(2,5-pdc)₂(tpha)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3) and {[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=pyridine-2,5-dicarboxylate, tp=p-phthalate, C₆H₅COO=benzoate, Imh=imidazole, NO₂C₆H₄COO=p-nitrobenzoate, N(CH₂COO)₃=nitrilotriacetate], were synthesized by hydrothermal method. Their structures were determined by single-crystal X-ray diffraction. At room temperature, the IR, UV-Vis-NIR and emission spectra of the four complexes were measured and analyzed. The four complexes exhibit the characteristic emission bands of the Sm³⁺ ion in the visible or NIR region, which should be attributed to the sensitization from the Zn-ligand(d-block) and ligands after forming coordination complexes. In addition, the sensitization from different ligands and d-block to Sm³⁺ ion was discussed, the shift, split and broad of the NIR emission bands were analyzed.

Key words: Sm3+ coordination complex, Crystal structure, Luminescent property

中图分类号:

O614.33

TrendMD:

迟玉贤, 邱菊青, 李淑梅, 杨艳红, 金晶, 牛淑云. 系列Sm³⁺配合物的合成、结构及光物理性能. 高等学校化学学报, 2014, 35(8): 1620.

CHI Yuxian, QIU Juqing, LI Shumei, YANG Yanhong, JIN Jing, NIU Shuyun. Syntheses, Structures and Photophysical Properties of a Series of Sm³⁺ Coordination Complexes^†. Chem. J. Chinese Universities, 2014, 35(8): 1620.

图/表 16

Table 1 Crystal data and structure refinement for complexes 1—4

Complex	1	2	3	4
Empirical formula	C₁₈H₁₄N₂ $O 1 3$ SmZn	C₃₈H₃₁N₂O₁₁SmZn	C₄₂H₃₄N₆O₂₉Sm₂	C₆H₁₂NO₉Sm
Formula mass	682.03	907.37	1387.45	392.52
Crystal system	Monoclinic	Triclinic	Triclinic	Orthorhombic
Space group	P2₁/c	P $1 ˉ$	P $1 ˉ$	Pbca
a/nm	0.99546(10)	1.0887(2)	0.9410(3)	0.81136(13)
b/nm	2.2139(2)	1.3527(3)	1.5371(5)	1.3133(2)
c/nm	0.97660(10)	1.3910(3)	1.8882(7)	2.0779(3)
α/(°)	90	70.219(2)	75.188(4)	90
β/(°)	102.6150(10)	84.491(2)	80.863(4)	90
γ/(°)	90	74.755(2)	78.084(4)	90
V/nm³	2.1003(4)	1.8597(6)	2.5670(15)	2.2140(6)
Z, D_c/(g·cm^-1)	4, 2.157	2, 1.620	2, 1.795	8, 2.355
μ/mm^-1	3.987	2.271	2.366	5.344
F(000)	1328	906	1368	1512
θ range/(°)	1.84—25.99	1.94—26.00	2.23—26.00	3.10—26.00
Data/restraints/parameters	4094/7/336	7147/15/526	9785/20/808	2166/6/203
Reflections collected/unique	11268/4094 (R_int=0.0309)	10096/7147 (R_int=0.0185)	13736/9785 (R_int=0.0263)	11059/2166 (R_int=0.0344)
GOF on F²	1.126	1.033	1.047	1.002
R₁, wR₂ [I>2σ(I)]	0.0288, 0.0733	0.0324, 0.0814	0.0478, 0.1129	0.0183, 0.0450
R₁, wR₂(All data)	0.0356, 0.0763	0.0387, 0.0845	0.0660, 0.1217	0.0244, 0.0477
Largest diff. peak and hole/( e·nm^-3)	657, -958	725, -867	1932, -1148	397, -422

Table 1 Crystal data and structure refinement for complexes 1—4

Complex	1	2	3	4
Empirical formula	C₁₈H₁₄N₂ $O 1 3$ SmZn	C₃₈H₃₁N₂O₁₁SmZn	C₄₂H₃₄N₆O₂₉Sm₂	C₆H₁₂NO₉Sm
Formula mass	682.03	907.37	1387.45	392.52
Crystal system	Monoclinic	Triclinic	Triclinic	Orthorhombic
Space group	P2₁/c	P $1 ˉ$	P $1 ˉ$	Pbca
a/nm	0.99546(10)	1.0887(2)	0.9410(3)	0.81136(13)
b/nm	2.2139(2)	1.3527(3)	1.5371(5)	1.3133(2)
c/nm	0.97660(10)	1.3910(3)	1.8882(7)	2.0779(3)
α/(°)	90	70.219(2)	75.188(4)	90
β/(°)	102.6150(10)	84.491(2)	80.863(4)	90
γ/(°)	90	74.755(2)	78.084(4)	90
V/nm³	2.1003(4)	1.8597(6)	2.5670(15)	2.2140(6)
Z, D_c/(g·cm^-1)	4, 2.157	2, 1.620	2, 1.795	8, 2.355
μ/mm^-1	3.987	2.271	2.366	5.344
F(000)	1328	906	1368	1512
θ range/(°)	1.84—25.99	1.94—26.00	2.23—26.00	3.10—26.00
Data/restraints/parameters	4094/7/336	7147/15/526	9785/20/808	2166/6/203
Reflections collected/unique	11268/4094 (R_int=0.0309)	10096/7147 (R_int=0.0185)	13736/9785 (R_int=0.0263)	11059/2166 (R_int=0.0344)
GOF on F²	1.126	1.033	1.047	1.002
R₁, wR₂ [I>2σ(I)]	0.0288, 0.0733	0.0324, 0.0814	0.0478, 0.1129	0.0183, 0.0450
R₁, wR₂(All data)	0.0356, 0.0763	0.0387, 0.0845	0.0660, 0.1217	0.0244, 0.0477
Largest diff. peak and hole/( e·nm^-3)	657, -958	725, -867	1932, -1148	397, -422

Fig.1 Asymmetric unit of complex 1

Fig.2 3D network of complex 1

Fig.3 Molecular structure of complex 2

Fig.4 1D hydrogen bonding chain of complex 2 along b direction

Fig.5 Asymmetric unit of complex 3

Fig.6 1D chain of complex 3 along a direction

Fig.7 Asymmetric unit of complex 4

Fig.8 2D layer of complex 4 in ab plane Water molecules are omitted for clarity.

Table 2 Assignments of absorption bands for the UV-Vis-NIR spectra of complexes 1—4

Assignment(theoretical value)	λ/nm(Complex 1)	λ/nm(Complex 2)	λ/nm(Complex 3)	λ/nm(Complex 4)
⁶H_5/2→⁶F_3/2(1516 nm)	1478, 1538	1502, 1554	1512, 1558	1484, 1516
⁶H_5/2→⁶F_5/2(1411 nm)	1370	1392	1394	1378
⁶H_5/2→⁶F_7/2(1260 nm)	1224	1240	1244	1232
⁶H_5/2→⁶F_9/2(1100 nm)	1074	1082	1082	1078
⁶H_5/2→⁶F_11/2(955 nm)	936	942	942	940
⁶H_5/2→⁴G_7/2(501 nm)	472	476	470	478
⁶H_5/2→⁴F_7/2(404 nm)	402	402		404
⁶H_5/2→⁴F_9/2(361 nm)				373
π→π^*	270, 370	266, 342	254, 318

Fig.9 Visible emission spectra of complex 1(a, λex=400 nm), pyridine-2,5-dicarboxylic acid(b, λex=397 nm) and p-phthalic acid(c, λex=349 nm)

Fig.10 Visible emission spectra of complex 2(a, λex=404 nm), benzoic acid(b, λex=260 nm) and imidazole(c, λex=350 nm)

Fig.11 Visible emission spectra of complex 3(a, λex=403 nm) and p-nitrobenzoic acid(b, λex=403 nm)

Fig.12 Visible emission spectra of complex 4(a, λex=403 nm) and aminotriacetic acid(b, λex=403 nm)

Fig.13 NIR emission spectra of complexes 1(A, λex=430 nm), 2(B, λex=404 nm), 3(C, λex=405 nm) and 4(D, λex=404 nm)

Fig.14 XRD patterns of complexes 1(A), 2(B), 3(C) and 4(D)

参考文献 37

[1]	Lakshminarayana1 G., Yang R., Qiu J. R., Brik M. G., Kumar G. A., Kityk I. V., J. Phys. D: Appl. Phys., 2009, 42, 1—12
[2]	Lin C. C., Tang Y. S., Hu S. F., Liu R. S., J. Lumin., 2009, 129, 1682—1684
[3]	Chen Y., Wang J., Liu C., Kuang X., Su Q., Appl. Phys. Lett., 2011, 98, 081917-1—081917-3
[4]	Du Y. Y., Huang K. K., Zhang J. Q., Wang C. C., Chu X. F., Hou C. M., Feng S. H., Chem. J. Chinese Universities, 2013, 34(3), 509—513
	(杜燕燕, 黄科科, 张佳旗, 王楚楚, 初学峰, 侯长民, 冯守华. 高等学校化学学报, 2013, 34(3), 509—513)
[5]	Jiang Y. Y., Liu G. X., Wang J. X., Dong X. T., Yu W. S., Chem. J. Chinese Universities, 2013, 34(4), 794—799
	(姜营营, 刘桂霞, 王进贤, 董相廷, 于文生. 高等学校化学学报, 2013, 34(4), 794—799)
[6]	Sun J., Liu Z., Du H., J. Rare Earth, 2011, 29, 101—102
[7]	Som T., Karmakar B., Spect. Act. A, 2010, 75, 640—646
[8]	Xia Z., Chen D., J. Am. Ceram. Soc., 2010, 93, 1397—1401
[9]	Ding J., Bao J., Sun S., Luo Z., Gao C., J. Comb. Chem., 2009, 11, 523—526
[10]	Xiao Z. H., Tan S. T., Wang X. Y., Zou Y. P., Spectroscopy and Spectral Analysis, 2005, 25, 145—148
	(肖尊宏, 谭松庭, 王霞瑜, 邹应萍. 光谱学与光谱分析, 2005, 25, 145—148)
[11]	Wang G., Qin W., Zhang D., Wang L., Wei G., Zhu P., Kim R., J. Phys. Chem. C, 2008, 112, 17042—17045
[12]	Yu M., Lin J., Wang Z., Fu J., Wang S., Zhang H. J., Han Y. C., Chem. Mater., 2002, 14, 2224—2231
[13]	Fan W., Bu Y., Song X., Sun S., Zhao X., Crystal Growth & Design, 2007, 7, 2361—2366
[14]	Hou Z., Yang P., Li C., Wang L., Lian H., Quan Z., Lin J., Chem. Mater., 2008, 20, 6686—6696
[15]	Grubisic A., Ko Y. J., Wang H., Bowen K. H., J. Am. Chem. Soc., 2009, 131, 10783—10790
[16]	Petoud S., Cohen S. M., Bünzli J. C. G., Raymond K. N., J. Am. Chem. Soc., 2003, 125, 13324—13325
[17]	Chi Y. X., Niu S. Y., Jin J., Inorg. Chim. Acta, 2009, 362, 3821—3828
[18]	Bassett A. P., Magennis S. W., Glover P. B., Lewis D. J., Spencer N., Parsons S., Williams R. M., Cola L. D., Pikramenou Z., J. Am. Chem. Soc., 2004, 126, 9413—9424
[19]	Quici S., Cavazzini M., Marzanni G., Accorsi G., Armaroli N., Ventura B., Barigelletti F., Inorg. Chem., 2005, 44, 519—537
[20]	Wang H., Yang J., Zhang C. M., Lin J., J. Solid State Chem., 2009, 182, 2716—2724
[21]	Jia G., You H., Yang M., Zhang L., Zhang H., J. Phys. Chem. C, 2009, 113, 16638—16644
[22]	Petoud S., Cohen S. M., Bünzli J. C. G., Raymond K. N., J. Am. Chem. Soc., 2003, 125, 13324—13325
[23]	Petoud S., Muller G., Moore E. G., Xu J., Sokolnicki J., Riehl J. P., Le U. N., Cohen S. M., Raymond K. N., J. Am. Chem. Soc., 2007, 129, 77—83
[24]	Yu J., Zhou L., Zhang H., Zheng Y., Li H., Deng R., Peng Z., Li Z., Inorg. Chem., 2005, 44, 1611—1618
[25]	Fang J., You H., Chen J., Lin J., Ma D., Inorg. Chem., 2006, 45, 3701—3704
[26]	Sun S. J., Zhang D. H., Zhang J. J., Ye H. M., Wang S. P., Wu K. Z., J. Mol. Struc., 2010, 977, 17—25
[27]	Jin Y., Zhang J., Lu S., Zhao H., Zhang X., Wang X. J., J. Phys. Chem. C, 2008, 112, 5860—5864
[28]	Huhtinen P., Kivelä M., Kuronen O., Hagren V., Takalo H., Tenhu H., Lävgren T., Härmä H., Anal. Chem., 2005, 77, 2643—2648
[29]	Çolak A. T., Yesilel O. Z., Pamuk G., Günay H., Büyükgüngör O., Polyhedron, 2011, 30, 1012—1022
[30]	Geranmayeh S., Abbasi A., Skripkin M. Y., Badiei A., Polyhedron, 2012, 45, 204—212
[31]	Bai Y. Y., Huang Y., Yan B., Song Y. S., Weng L. H., Inorg. Chem. Commun., 2008, 11, 1030—1032
[32]	Deacon G. B., Phillips R. J., Coord. Chem. Rev., 1980, 33, 227—250
[33]	Kumari N., Ward B. D., Kar S., Mishra L., Polyhedron, 2012, 33, 425—434
[34]	Zhang J. L., Chen B. W., Luo X., Du K., Chem. Res. Chinese Universities, 2012, 28(6), 1054—1057
[35]	Li Y. X., Xue M., Guo L. J., Huang L., Chen S. R., Qiu S. L., Chem. Res. Chinese Universities, 2013, 29(2), 196—200
[36]	Shuvaev S., Utochnikova V., Marciniak Ł., Freidzon A., Sinev I., Deun R. V., Freire R. O., Zubavichus Y., Grünert W., Kuzmina N., Dalton Trans., 2014, 43, 3121—3136
[37]	Maxim C., Branzea D. G., Tiseanu C., Rouzières M., Clérac R., Andruh M., Avarvari N., Inorg. Chem., 2014, 53, 2708—2717

系列Sm³⁺配合物的合成、结构及光物理性能

Syntheses, Structures and Photophysical Properties of a Series of Sm³⁺ Coordination Complexes^†

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