Luminescence Sensing of Benzaldehyde and Cation of 3-(2-Carboxy-phenoxy)-phthalicate-based Lanthanide Complexes†

doi:10.7503/cjcu20160126

Abstract

Abstract:

Five lanthanide-organic frameworks, [Sm₂(bdbc)₂(phen)₄](1) and [Ln(bdbc)(phen)·(H₂O)][Ln=Eu(2), Gd(3), Tb(4), Dy(5), bdbc=3-(2-carboxy-phenoxy)phthalicate, phen=1,10-phenanthroline], have been synthesized and determined by X-ray single-crystal diffraction. Complex 1 is a binuclear molecule and forms a one-dimensional(1D) supramolecular architecture via hydrogen and C—H…π bonds. Complexes 2—5 are isostructural and display a one-dimensional(1D) chain structure, which form a three-dimensional(3D) supramolecular architecture via hydrogen and C—H…π bonds. Complexes 1, 2, 4 and 5 present the characteristic emission of Sm³⁺, Eu³⁺, Tb³⁺ and Dy³⁺, which are attributed to ⁴G_5/2→⁶H_J_/2(J=5, 7, 9) transitions of Sm³⁺, ⁵D₀→⁷F_J(J=1—4) transitions of Eu³⁺, ⁵D₄→⁷F_J(J=6, 5, 4, 3) transitions of Tb³⁺, ⁴F_5/2→⁶H_J_/2(J=15, 13) transitions of Dy³⁺, respectively. Furthermore, the luminescence properties of complex 4 were investigated. The results show that complex 4 may be used as a fluorescent probe to detect cation in aqueous solution and benzaldehyde.

Key words: Lanthanide complex, Fluorescent probe, Cation, Benzaldehyde

CLC Number:

O614
O641.4

TrendMD:

DONG Gaoyun,LI Rui,FAN Tingting,LI Jiajia,LI Xia. Luminescence Sensing of Benzaldehyde and Cation of 3-(2-Carboxy-phenoxy)-phthalicate-based Lanthanide Complexes^†[J]. Chem. J. Chinese Universities, 2016, 37(8): 1421.

Figures/Tables 11

Table 1 Crystallographic data of complexes 1—5

Compound	1	2	3	4	5
Empirical formula	C₇₈H₄₆N₈O₁₄Sm₂	C₂₇H₁₇N₂O₈Eu	C₂₇H₁₇N₂O₈Gd	C₂₇H₁₇N₂O₈Tb	C₂₇H₁₇N₂O₈Dy
Formula weight	1619.93	649.39	654.67	656.34	659.92
Temperature/K	296(2)	296(2)	296(2)	296(2)	296(2)
Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic	Monoclinic
Space group	C2/c	P2₁/n	P2₁/n	P2₁/n	P2₁/n
a/nm	2.79501(11)	1.17504(5)	1.17519(4)	1.1732(2)	1.17249(4)
b/nm	1.33737(5)	1.04560(4)	1.04434(4)	1.0427(2)	1.04125(4)
c/nm	2.30816(15)	2.01377(8)	2.01048(7)	2.0085(4)	2.00662(7)
β/(°)	121.4560(10)	96.7414(11)	96.8519(11)	96.86(3)	96.8906(10)
V/nm³	7.3599(6)	2.45706(17)	2.44983(15)	2.4394(9)	2.43210(15)
Z	4	4	4	4	4
D_c/(Mg·m^-3)	1.462	1.755	1.775	1.787	1.802
Absorption coefficient/mm^-1	1.649	2.608	2.763	2.955	3.128
F(000)	3224	1280	1284	1288	1292
Crystal size/mm	0.328×0.069×0.056	0.411×0.359×0.189	0.339×0.204×0.156	0.296×0.230×0.101	0.382×0.116×0.091
θ range for data collection /(°)	2.98—24.51	3.19—27.49	3.19—27.55	3.451—25.098	3.20—27.50
Limiting indices	-36≤h≤36, -17≤k≤17, -29≤l≤30	-14≤h≤13, -12≤k≤12, -24≤l≤24	-14≤h≤13, -12≤k≤12, -23≤l≤23	-14≤h≤13, -12≤k≤12, -23≤l≤23	-13≤h≤13, -12≤k≤12, -23≤l≤23
Reflections collected/unique	75545/6539	31331/4367	31544 / 4354	32542 / 4341	31358 / 4324
R_int	0.0920	0.0256	0.0280	0.0291	0.0326
Completeness(%)	99.6	99.8	99.8	99.8	99.8
Data/restraints/parameters	8519/0/460	4367/1/353	4354/1/353	4331/1/353	4324/1/353
Goodness-of-fit on F²	1.037	1.064	1.037	1.082	1.076
Final R indices[I>2σ(I)]	R₁=0.1082, wR₂=0.0991	R₁=0.0225, wR₂=0.0471	R₁=0.0240, wR₂=0.0434	R₁=0.0229, wR₂=0.0441	R₁=0.0288, wR₂=0.0459
R indices(all data)	R₁=0.0440, wR₂=0.0833	R₁=0.0194, wR₂ =0.0451	R₁=0.0191, wR₂=0.0411	R₁=0.0182, wR₂=0.0420	R₁=0.0210, wR₂=0.0432
CCDC No.	1052818	1052814	1052845	1052846	1052875

Table 1 Crystallographic data of complexes 1—5

Compound	1	2	3	4	5
Empirical formula	C₇₈H₄₆N₈O₁₄Sm₂	C₂₇H₁₇N₂O₈Eu	C₂₇H₁₇N₂O₈Gd	C₂₇H₁₇N₂O₈Tb	C₂₇H₁₇N₂O₈Dy
Formula weight	1619.93	649.39	654.67	656.34	659.92
Temperature/K	296(2)	296(2)	296(2)	296(2)	296(2)
Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic	Monoclinic
Space group	C2/c	P2₁/n	P2₁/n	P2₁/n	P2₁/n
a/nm	2.79501(11)	1.17504(5)	1.17519(4)	1.1732(2)	1.17249(4)
b/nm	1.33737(5)	1.04560(4)	1.04434(4)	1.0427(2)	1.04125(4)
c/nm	2.30816(15)	2.01377(8)	2.01048(7)	2.0085(4)	2.00662(7)
β/(°)	121.4560(10)	96.7414(11)	96.8519(11)	96.86(3)	96.8906(10)
V/nm³	7.3599(6)	2.45706(17)	2.44983(15)	2.4394(9)	2.43210(15)
Z	4	4	4	4	4
D_c/(Mg·m^-3)	1.462	1.755	1.775	1.787	1.802
Absorption coefficient/mm^-1	1.649	2.608	2.763	2.955	3.128
F(000)	3224	1280	1284	1288	1292
Crystal size/mm	0.328×0.069×0.056	0.411×0.359×0.189	0.339×0.204×0.156	0.296×0.230×0.101	0.382×0.116×0.091
θ range for data collection /(°)	2.98—24.51	3.19—27.49	3.19—27.55	3.451—25.098	3.20—27.50
Limiting indices	-36≤h≤36, -17≤k≤17, -29≤l≤30	-14≤h≤13, -12≤k≤12, -24≤l≤24	-14≤h≤13, -12≤k≤12, -23≤l≤23	-14≤h≤13, -12≤k≤12, -23≤l≤23	-13≤h≤13, -12≤k≤12, -23≤l≤23
Reflections collected/unique	75545/6539	31331/4367	31544 / 4354	32542 / 4341	31358 / 4324
R_int	0.0920	0.0256	0.0280	0.0291	0.0326
Completeness(%)	99.6	99.8	99.8	99.8	99.8
Data/restraints/parameters	8519/0/460	4367/1/353	4354/1/353	4331/1/353	4324/1/353
Goodness-of-fit on F²	1.037	1.064	1.037	1.082	1.076
Final R indices[I>2σ(I)]	R₁=0.1082, wR₂=0.0991	R₁=0.0225, wR₂=0.0471	R₁=0.0240, wR₂=0.0434	R₁=0.0229, wR₂=0.0441	R₁=0.0288, wR₂=0.0459
R indices(all data)	R₁=0.0440, wR₂=0.0833	R₁=0.0194, wR₂ =0.0451	R₁=0.0191, wR₂=0.0411	R₁=0.0182, wR₂=0.0420	R₁=0.0210, wR₂=0.0432
CCDC No.	1052818	1052814	1052845	1052846	1052875

Fig.1 Coordination environment of Sm3+ in complex 1(A) and 1D chain structure of complex 1 via the hydrogen bonds and C—H…π interactions(B)

Fig.2 Coordination environment of Eu3+ in complex 2(A), 1D chain structure(B) and 3D supramolecular structure via the hydrogen bonds and C—H…π interactions(C) of complex 2

Fig.3 Emission spectra of complex 3(a) and free ligands phen(b) and bdbc(c)

Fig.4 Excitation(B, D) and emission(A, C) spectra of complexes 2(A, B) and 4(C, D)(B) a. λex=352 nm; b. λex=397 nm; (D) a. λex=350 nm; b. λex=380 nm.

Fig.5 Emission spectra(A) and the 5D4→7F5 transition intensities(B) of complex 4 in the presence of different cations(10-2 mol/L) a. H2O; b. K+; c. Ca2+; d. Li+; e. Mg2+; f. Na+; g. Pb2+; h. Ba2+; i. Zn2+; j. Al3+; k. Cd2+; l. Ni2+; m. Cu2+; n. Ag+; o. Co2+; p. Cr2+; q. Fe3+.

Fig.6 Emission spectra(A) and the 5D4→7F5 transition intensities(B) of complex 4 in the presence of different concentrations of Co2+(λex=350 nm) c(Co2+)/(mol·L-1): a. 0; b. 5×10-6; c. 1×10-5; d. 1×10-4; e. 1×10-3; f. 5×10-3; g. 5×10-2.

Fig.7 Emission spectra(A) and 5D4→7F5 transition intensities(B) of complex 4 in the presence of different concentrations of Fe3+(λex=350 nm) c(Fe3+)/(mol·L-1): a. 0; b. 5×10-6; c. 1×10-5; d. 1×10-4; e. 1×10-3; f. 5×10-3; g. 5×10-2.

Fig.8 Emission spectra(A, B) and 5D4→7F5 transition intensity(insets) of complex 4 dispersed in different solvents(λex=350 nm) (A) a. EtOAc; b. acetone; c. benzene. (B) a. Benzene; b. dichloromethane; c. methanol; d. formamide; e. dimethylbenzene; f. acetonitrile; g. DMF; h. formaldeltyde; i. benzaldehyde.

Fig.9 Emission spectra(A) and 5D4→7F5 transition intensity(B) of complex 4 dispersed in EtOAc with different concentrations of benzaldehyde(λex=350 nm) c(Benzaldehyde)/(mol·L-1): a. 10-6; b. 5×10-5; c. 10-4; d. 2×10-4; e. 3×10-4; f. 5×10-4; g. 6×10-4; h. 8×10-4.

Fig.10 TG curves of complexes 1—5(a—e)

References 32

[1]	Pramanik, S. , Zheng, C. , Zhang, X. , Emge T., J. , Li, J. , J. Am. Chem. Soc., 2011, 133, 4153- 4155 doi: 10.1021/ja106851d URL pmid: 21384862
[2]	Ma L., Q. , Abney, C. , Lin, W. , Chem. Soc. Rev., 2009, 38, 1248- 1256
[3]	Lee J., Y. , Farha O., K. , Roberts, J. , Scheidt K., A. , Nguyen S., T. , Hupp J., T. , Chem. Soc. Rev., 2009, 38, 1450- 1459 doi: 10.1039/b807080f URL
[4]	Hao J., N. , Yan, B. , Chem. Commun., 2015, 51, 7737- 7740 doi: 10.1007/s12035-015-9439-0 URL pmid: 26392295
[5]	Zhang Z., J. , Xiang S., C. , Rao X., T. , Zheng, Q. , Fronczek F., R. , Qian G., D. , Chen B., L. , Chem. Commun., 2010, 46, 7205- 7207 doi: 10.1039/c0cc01236j URL pmid: 20737107
[6]	Li J., R. , Kuppler R., J. , Zhou H., C. , Chem. Soc. Rev., 2009, 38, 1477- 1504
[7]	Wang Y., N. , Zhang, P. , Yu J., H. , Xu J., Q. , Dalton Trans., 2015, 44, 1655- 1663 doi: 10.1186/s12885-015-1887-4 URL pmid: 26541196
[8]	Feng, X. , Wang Y., Y. , Hu Y., C. , Chen S., P. , Zhao W., J. , Yang X., W. , J. Coord. Chem., 2012, 65, 2692- 2704
[9]	Wang, L. , Acta Cryst., 2013, 69, 101- 107
[10]	Zhang S., Q. , Jiang F., L. , Wu M., Y. , Ma, J. , Bu, Y. , Hong M., C. , Cryst. Growth Des., 2012, 12, 1452- 1463 doi: 10.1021/cg201556b URL
[11]	Wang H., L. , Zhang D., P. , Sun D., F. , Chen Y., T. , Zhang L., F. , Tian L., J. , Jiang J., Z. , Ni Z., H. , Cryst. Growth Des., 2009, 9, 5273- 5282 doi: 10.3959/1536-1098-63.1.27 URL
[12]	Wu, H. , Yang, J. , Su Z., M. , Batten S., R. , Ma J., F. , J. Am. Chem. Soc., 2011, 133, 11406- 11409 doi: 10.1021/ja202303b URL pmid: 21728370
[13]	Kong C., Y. , J. Inorg. Organomet. Polym. Mater., 2011, 21, 189- 194 doi: 10.1039/C1JM13551A URL
[14]	Celedonio M., A. , Lucia A., M. , Raul G., R. , Eur. J. Inorg. Chem., 2015, 29, 4921- 4934 doi: 10.1002/ejic.201500776 URL
[15]	Marchand, A. , Granzhan, A. , Iida, K. , Tsushima, Y. , Ma, Y. , Nagasawa, K. , Teulade-Fichou, M. , Gabelica, Valerie. , J. Am. Chem. Soc., 2015, 137, 750- 756 doi: 10.1021/ja5099403 URL pmid: 25525863
[16]	Accorsi, G. , Listorti, A. , Yoosaf, K. , Armaroli, N. , Chem. Soc. Rev., 2009, 38, 1690- 1700 doi: 10.1039/b806408n URL pmid: 19587962
[17]	Bauer C., A. , Timofeeva T., V. , Settersten T., B. , Patterson B., D. , Liu V., H. , Simmons B., A. , Allendorf M., D. , J. Am. Chem. Soc., 2007, 129, 7136- 7144
[18]	Saleem, M. , Lee K., H. , RSC Adv., 2015, 5, 72150- 72287 doi: 10.1039/C5RA13831K URL
[19]	Novio, F. , Simmchen, J. , Vazquez-Mera, N. , Amorin-Ferre, L. , Ruiz-Molina D., C. , Chem. Rev., 2013, 257, 2839- 2847 doi: 10.1016/j.ccr.2013.04.022 URL
[20]	徐布一, 叶懿, 阮若云, 颜有仪, 廖林川. 高等学校化学学报, 2015, 36( 9), 1667- 1673 doi: 10.7503/cjcu20150228
	Xu B., Y. , Ye, Y. , Ruan R., Y. , Yan Y., Y. , Liao L., C. , Chem. J. Chinese Universities, 2015, 36( 9), 1667- 1673 doi: 10.7503/cjcu20150228
[21]	徐惠, 代艳娜, 单洪岩, 费强, 郇延富, 李光华, 冯国栋. 高等学校化学学报, 2014, 35( 4), 736- 740 doi: 10.7503/cjcu20131096
	Xu, H. , Dai Y., N. , Shan H., Y. , Fei, Q. , Huan Y., F. , Li G., H. , Feng G., D. , Chem. J. Chinese Universities, 2014, 35( 4), 736- 740 doi: 10.7503/cjcu20131096
[22]	Zhao, B. , Chen X., Y. , Cheng, P. , Liao D., Z. , Yan S., P. , Jiang Z., H. , J. Am. Chem. Soc., 2004, 126, 15394- 15395
[23]	Harbuzaru B., V. , Corma, A. , Rey, F. , Atienzar, P. , Ananias, D. , Carlos L., D. , Rocha, J. , Angew. Chem. Int. Ed., 2008, 47, 1080- 1083 doi: 10.1002/anie.200704702 URL pmid: 18183561
[24]	赵秀巧, 王会, 董丽君, 徐庆红. 高等学校化学学报, 2013, 34( 6), 1318- 1326 doi: 10.7503/cjcu20121156
	Zhao X., Q. , Wang, H. , Dong L., J. , Xun Q., H. , Chem. J. Chinese Universities, 2013, 34( 6), 1318- 1326 doi: 10.7503/cjcu20121156
[25]	Zhou, Y. , Chen H., H. , Yan, B. , J. Mater. Chem. A., 2014, 2, 13691- 13697
[26]	Hao J., N. , Yan, B. , Chem. Commun., 2015, 51, 7737- 7740 doi: 10.1007/s12035-015-9439-0 URL pmid: 26392295
[27]	Shi B., B. , Zhong Y., H. , Guo L., L. , Dalton Trans., 2015, 44, 4362- 4369 doi: 10.1039/c4dt03326d URL pmid: 25641054
[28]	Sheldrick G., M. , SHELXS 97, Program for Crystal Structure Solution, University of Göttingen, Göttingen, 1997
[29]	Sheldrick G., M. , SHELXL 97, Program for Crystal Structure Refinement, University of Göttingen, Göttingen, 1997
[30]	Gore A., H. , Gunjal D., B. , Kokate M., R. , Sudarsan, V. , Anbhule P., V. , Patil S., R. , Kolekar G., B. , ACS Appl. Mater. Interfaces, 2012, 4, 5217- 5226 doi: 10.1021/am301136q URL pmid: 22948013
[31]	Zhou, Y. , Chen H., H. , Yan, B. , J. Mater. Chem. A, 2014, 2, 13691- 13697
[32]	Xiang, Z. , Fang, C. , Leng, S. , Cao, D. , J. Mater. Chem. A, 2014, 2, 7662- 7665 doi: 10.1016/j.ica.2014.09.015 URL