Synthesis, Structure and Electrochemical Properties of Metal Cobalt Complexes with Interpenetrating Structures†

doi:10.7503/cjcu20170650

Abstract

Abstract:

Using multidenate 4,4'-(phenylazanediyl)dibenzoic acid(H₂L) and 1,3-bis(imidazol-l-yl)benzene(B), 3,5-bis(imidazol-l-yl)pyridine(bimp) or 1,4-bis(imidazol-l-yl)benzene(B') as ligands under solvothermal conditions, three new metal-organic frameworks with interpenetrating structure, {[CoLB]·H₂O}_n(1), {[Co₂L₂(bimp)_0.5]·3H₂O}_n(2) and {[Co₂L₂B'₂]·2DMF}_n(3), were synthesized. The complexes were characterized by single-crystal X-ray diffraction(XRD), thermal analysis and powder X-ray diffraction(PXRD). Complexes 1—3 all crystallize in the monoclinic system, with C2/c(complex 1), P2/n(complex 2) and P2₁(complex 3) space group, respectively. In complexes 1 and 3, Co²⁺ forms a tetracoordinate geometry, whereas it forms a five-coordinated geometric configuration and exists as a dual-core paddle-shaped structural unit [Co₂(CO₂)₄] in complex 2. Complexes 1 and 2 give a 2-fold interpenetrating three-dimensional(3D) supramolecular networks, while complex 3 exhibits a 4-fold interpenetrating 3D framework. The results of electrochemical studies show that complexes 1—3 are electrochemically active substances with good electrochemical reversibility.

Key words: Metal-organic framework(MOF), Cobalt complex, Interpenetrating structure, Cyclic voltammetry

TrendMD:

ZHAO Changjiang,LIU Xin,TIAN Li,ZHAO Lun. Synthesis, Structure and Electrochemical Properties of Metal Cobalt Complexes with Interpenetrating Structures^†[J]. Chem. J. Chinese Universities, 2018, 39(5): 861.

Figures/Tables 9

Fig.1 Molecular structures of the ligands

Table 1 Crystal data and structure refinement of complexes 1—3

Complex	1	2	3
CCDC No.	1575252	1575253	1575254
Molecular formula	C₃₂H₂₅CoN₅O₅	C₅₁H₄₇Co₂N₇O₁₃	C₇₀H₆₀Co₂N₁₂O₁₀
F_w	618.51	1083.82	1347.16
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	C2/c	P2/n	P2₁
a/nm	2.7443(10)	1.58338(11)	1.1130(3)
b/nm	1.0762(4)	0.86972(6)	2.1039(5)
c/nm	2.2217(9)	1.75432(12)	2.6929(7)
α/(°)	90.00	90.00	90.00
β/(°)	90.12	94.5160(10)	90.00
γ/(°)	90.00	90.00	90.12
V/nm³	6.562(4)	2.4084(3)	6.306(3)
Z	8	2	4
D_c/(g·cm^-3)	1.252	1.495	1.419
F(000)	2552	1120	2792
GOF on F²	0.916	1.058	0.851
R₁, wR₂[I>2σ(I)]	0.0815, 0.2116	0.0565, 0.1562	0.0744, 0.1334
R₁, wR₂(all data)	0.1462, 0.2308	0.1060, 0.1971	0.2324, 0.1822

Fig.2 Coordination environment of the Co(Ⅱ) ions(A) and views of 2D sheets(B), 3D framework(C), topology network(D) and the two-fold interpenetrating framework(E) of complex 1 The hydrogen atoms are omitted for clarity. Symmetry codes: #1. x-1/2, y+1/2, z; #2. x, -y-1, z+1/2; #3. x+1/2, y-1/2, z; #4. x, -y-1, z-1/2.

Fig.3 Coordination environment of the Co(Ⅱ) ions(A) and views of 2D sheets(B), 3D framework(C), topology of 3D framework(D), two-fold interpenetrating framework(E) and the helical chains(F) of complex 2 The hydrogen atoms are omitted for clarity. Symmetry codes: #1. -x+3/2, y, -z+3/2; #2. -x+3/2, y+1, -z+1/2; #3. x-1/2, -y+2, z-1/2; #4. -x+2, -y+1, -z+1; #5. x+1/2, -y+2, z+1/2; #6. -x+3/2, y-1, -z+1/2; #7. -x+3/2, y, -z+1/2.

Fig.4 Coordination environment of Co(Ⅱ) ions(A) and views of 3D framework(B), topology network of 3D framework(C), four-fold interpenetrating framework(D) and the two different helical chains(E, F) of complex 3 The hydrogen atoms are omitted for clarity. Symmetry codes: #1. -x+5/2, y+1/2, -z+3/2; #2. x-2, y, z; #3. -x+5/2, y-1/2, -z+3/2; #4. x+2, y, z; #5. -x+1/2, y-1/2, -z+1/2; #6. -x+1/2, y+1/2, -z+1/2.

Fig.5 Experimental(a) and simulated(b) PXRD patterns of complex 1(A), complex 2(B) and complex 3(C)

Fig.6 TG curves of complexes 1(a), 2(b) and 3(c)

Fig.7 Cyclic voltammograms of complex 1(A), complex 2(B) and complex 3(C)

Fig.8 Cyclic voltammograms at different sweep speeds(A) and I-v1/2 plots(B) of complex 1(A, A'), complex 2(B, B') and complex 3(C, C') (A)—(C) Scan rate/(mV·s-1): a. 50; b. 70; c. 90; d. 110; e. 130; f. 150; g. 170; h. 200.

References 44

[1]	Furukawa H., Cordova K.E., O’Keeffe M., Yaghi O. M., Science, 2013, 341(6149), 1230444
[2]	Huang C.T., Wu X. F., Li G. H., Gao L., Feng S. H., Chem. [J]. Chinese Universities, 2015, 36(9), 1661—1666
	(黄楚婷, 吴小峰, 李光华, 高路, 冯守华. 高等学校化学学报, 2015, 36(9), 1661—1666)
[3]	Shustova N.B., McCarthy B. D., Dinca M., [J]. Am. Chem. Soc., 2011, 133, 20126—20129
[4]	Zhao C.J., Zhao L., Zhang M., Inorg. Chim. Acta, 2018, 468, 136—143
[5]	Cao Y., Zhu Z., Xu J., Wang L., Sun J., Chen X., Fan Y., Dalton Trans., 2015, 44, 1942—1947
[6]	Zhao L., Guo H.D., Tang D., Zhang M., CrystEngComm, 2015, 17, 5451—5467
[7]	Hoskins B.F., Robson R. J., [J]. Am. Chem. Soc., 1989, 111(15), 5962—5964
[8]	Wang X.Y., Wang L., Wang Z. M., Gao S., [J]. Am. Chem. Soc., 2006, 128(3), 674—675
[9]	Guo D., Pang K.L., Duan C. Y., He C., Meng Q. [J]., Inorg. Chem., 2002, 41(23), 5978—5985
[10]	Li J.R., Ma Y., McCarthy M. C., Sculley J., Yu J., Jeong H. K., Balbuena P. B., Zhou H. C., Coord. Chem. Rev., 2011, 255, 1791—1823
[11]	He Y., Furukawa H., Wu C., O’Keeffe M., Krishna R., Chen B., Chem. Commun., 2013, 49, 6773—6775
[12]	Li D.S., Zhao J., Wu Y. P., Liu B., Bai L., Zou K., Du M., Inorg. Chem., 2013, 52, 8091—8098
[13]	Lee J., Farha O.K., Roberts J., Scheidt K. A., Nguyen S. T., Hupp J. T., Chem. Soc. Rev., 2009, 38, 1450—1459
[14]	Liu Y., Xuan W.M., Cui Y., Adv. Mater., 2010, 22(37), 4112—4135
[15]	Wei N., Zhang M.Y., Zhang X. N., Li G. M., Zhang X. D., Han Z. B., Cryst. Growth Des., 2014, 14, 3002—3009
[16]	Liu Y., Mo K., Cui Y., Inorg. Chem., 2013, 52, 10286—10291
[17]	Heine J., Muller-Buschbaum K., Chem. Soc. Rev., 2013, 42, 9232—9242
[18]	Jiang H.L., Feng D., Wang K., Gu Z. Y., Wei Z., Chen Y. P., Zhou H. C., [J]. Am. Chem. Soc., 2013, 135, 13934—13938
[19]	Zhu M., Hao Z.M., Song X. Z., Meng X., Zhao S. N., Song S. Y., Zhang H. [J]., Chem. Commun., 2014, 50, 1912—1914
[20]	Kreno L.E., Leong K., Farha O. K., Allendorf M., van Duyne R. P., Hupp J. T., Chem. Soc. Rev., 2012, 112(2), 1105—1125
[21]	Yamada T., Otsubo K., Makiura R., Kitagawa H., Chem. Soc. Rev., 2013, 42, 6655—6669
[22]	Yoon M., Suh K., Natarajan S., Kim K., Angew. Chem. Int.Ed., 2013, 52(10), 2688—2700
[23]	Ma L.F., Wang L. Y., Luand D. H., Batten S. R., Cryst. Growth Des., 2009, 9, 1741—1749
[24]	Liu D., Ren Z.G., Li H. X., Chen Y., Wang J., Zhang Y., Lang J. P., CrystEngComm, 2010, 12, 1912—1919
[25]	Long L.S., CrystEngComm, 2010, 12, 1354—1365
[26]	Gao L.J., Wang L., Wang S. Y., Jing S. B., Chem. [J]. Chinese Universities, 2016, 37(9), 1589—1595
	(高丽娟, 王莉, 王圣燕, 井淑波. 高等学校化学学报, 2016, 37(9), 1589—1595)
[27]	Hu F.L., Wang S. L., Wu B., Yu H., Wang F., Lang J. P., CrystEngComm, 2014, 16, 6354—6363
[28]	Sun Y.X., Sun W. Y., Chin. Chem. Lett., 2014, 25, 823—828
[29]	Liu L.L., Ren Z. G., Zhu L. W., Wang H. F., Yan W. Y., Lang J. P., Cryst. Growth Des., 2011, 11, 3479—3488
[30]	Cui G.H., Li J. R., Tian J. L., Bu X. H., Batten S. R., Cryst. Growth Des., 2005, 5, 1775—1780
[31]	Liu Q., Ren Z.G., Deng L., Zhang W. H., Zhao X., Sun Z. R., Lang J. P., Dalton Trans., 2015, 44, 130—137
[32]	Batten S.R., Robson R., Angew. Chem. Int. Ed., 1998, 37, 1460—1494
[33]	Batten S.R., CrystEngComm, 2001, 3, 67—72
[34]	Carlucci L., Ciani G., Proserpio D.M., Coord. Chem. Rev., 2003, 246, 247—289
[35]	Yang J., Ma J.F., Batten S. R., Chem. Commun., 2012, 48, 7899—7912
[36]	Zhou J.L., Wang Y. Y., Zhou M. J., Qin L., Zhang M. D., Yang Q. X., Zheng H. G., Inorg. Chem. Commun., 2014, 40, 148—150
[37]	Liu B., Zhang Q., Ding H., Hu G., Du Y., Wang C., Wu J., Li S., Zhou H., Yang J., Tian Y., Dyes Pigm., 2012, 95(1), 149—160
[38]	Sheldrick G.M., Acta Crystallogr. Sect. C: Cryst. Struc. Chem., 2015, 71, 3—8
[39]	Sheldrick G.M., Acta Crystallogr. Sect. A, 2008, 64, 112—122
[40]	Zhang Z.Y., Deng Z. P., Huo L. H., Zhao H., Gao S., Inorg. Chem., 2013, 52(10), 5914—5923
[41]	Huang R.Y., Wang J. W., Xue C., Zhao S. P., Xu H., Inorg. Chim. Acta, 2014, 423, 133—138
[42]	Fatma K., Bulent D., Sabriye P.O., Eser K., Dyes Pigm., 2010, 84(1), 14—18
[43]	Liu L.L., Huang J. J., Wang X. L., Liu G. C., Yang S., Lin H. Y., Inorg. Chim. Acta, 2013, 394, 715—722
[44]	Hao S.Y., Hou S. X., Van H. K., Cui G. H., Dalton Trans., 2017, 46(6), 1951—1962

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