Synthesis, Structures and Properties of Homochiral Coordination Polymers Assembled from Semirigid Lactic Acid Derivatives†

doi:10.7503/cjcu20160647

Abstract

Abstract:

Under the solvothermal reaction condition, two pairs of homochiral coordination polymers, namely [Cd₂((R)-CBA)₂(DPEE)(H₂O)₂]_n(1-D), [Cd₂((S)-CBA)₂(DPEE)(H₂O)₂]_n(1-L), [Cd((R)-CBA)(1,4-DIB)]·H₂O(2-D) and [Cd((S)-CBA)(1,4-DIB)]. H₂O(2-L)[DPEE=(E)-1,2-di(pyridin-4-yl)ethene; 1,4-DIB=1,4-di(1H-imidazol-1-yl)benzene; (R)-H₂CBA=(R)-4-(1-carboxyethoxy)benzoic acid; (S)-H₂CBA=(S)-4-(1-carboxyethoxy)benzoic acid], have been prepared from synthetic lactic acid derivative ligands[(R)-H₂CBA and(S)-H₂CBA], auxiliary ligands and Cd²⁺ ions. Among these complexes, 1-D and 1-L have ladder-like Cd-CBA^2- chains, which are further linked by DPEE ligands to form a 2D framework. Complexes 2-D and 2-L feature three-dimensional supramolecular structure with hydrogen bonds, containing three kinds of homochiral helical chains. Moreover, the thermal stabilities, solid-state circular dichroism(CD) and photoluminescent properties of the complexes were also investigated.

Key words: Semirigid lactic acid derivative, Homochiral, Coordination polymer, Helical chain

CLC Number:

O614.2

TrendMD:

XU Zhongxuan, ZHAO Guanglian, LUO Le, LONG Zhenmin. Synthesis, Structures and Properties of Homochiral Coordination Polymers Assembled from Semirigid Lactic Acid Derivatives^†[J]. Chem. J. Chinese Universities, 2017, 38(1): 12.

Figures/Tables 12

Scheme 1 Synthetic routes of four HCPs and structures of auxiliary ligands DPEE and 1,4-DIB

Table 1 Crystal data and refinement results for complexes 1-D, 1-L, 2-D and 2-L

Compound	1-D	1-L	2-D	2-L
Chemical formula	C₃₂H₃₀Cd₂N₂O₁₂	C₃₂H₃₀Cd₂N₂O₁₂	C₂₂H₂₀CdN₄O₆	C₂₂H₂₀CdN₄O₆
Molecular weight	859.41	859.41	548.83	548.83
Crystal system	Triclinic	Triclinic	Orthorhmbic	Orthorhmbic
a/nm	0.79969(4)	0.79362(3)	1.61472(5)	1.61199(9)
b/nm	0.94480(6)	0.93695(4)	1.68334(6)	1.68962(11)
c/nm	1.11730(7)	1.11630(4)	8.3019(3)	8.3055(5)
α/(°)	87.681(5)	87.855(3)	90	90
β/(°)	75.203(4)	75.212(3)	90	90
γ/(°)	71.788(5)	72.171(4)	90	90
Unit cell volume/nm³	0.77458(8)	0.76327(6)	2.25656(13)	2.2621(2)
Temperature/K	295.27(10)	293(2)	293(2)	293(2)
Space group	P1	P1	P2₁2₁2	P2₁2₁2
No. of formula units per unit cell, Z	1	1	4	4
Radiation type	Cu Kα	Mo Kα	Mo Kα	Mo Kα
Absorption coefficient, μ/mm^-1	11.605	1.464	1.014	1.011
No. of reflections measured	4800	11740	6672	16928
No. of independent reflections	3283	6688	4086	4840
R_int	0.0385	0.0258	0.0310	0.0249
Final R₁/wR(F²)values[I > 2σ(I)]	0.0562/0.1755	0.0264/0.0515	0.0411/0.0643	0.0258/0.0626
Final R₁/wR(F²) values(all data)	0.0569/0.1766	0.0297/0.0529	0.0546/0.0681	0.0287/0.0648
Goodness of fit on F²	1.059	0.894	1.006	1.002
Flack parameter	0.020(14)	-0.063(17)	-0.04(2)	0.018(9)
CCDC No.	1502336	1502337	1502338	1502339

Fig.1 Coordination environment of enantiomers 1-D(A) and 1-L(B)Symmetry codes: a. x, y, -1+z; b. x, -1+y, 1+z.

Fig.2 1D ladder-like chain constructed by Cd2+ ions and (R)-CBA2- ligands(A), 2D framework of 1-D composed of 1D Cd-(R)-CBA2- chains and DPEE ligands(B) and the sql net of 1-D(C)

Fig.3 Coordination environment of enantiomers 2-D(A) and 2-L(B) Symmetry codes: a. -0.5+x, 1.5-y, 1-z.

Fig.4 Left-handed helical A-chain in 2-D(A), right-handed helical A-chain in 2-L(B), left-handed helical B-chain in 2-D(C), right-handed helical B-chain in 2-L(D), 2D layer of 2-D constructed by left-handed helical A-chains and B-chains(E) and 2D layer of 2-L constructed by right-handed helical A-chains and B-chains(F)

Fig.5 Right-handed helical C-chain in 2-D(A), left-handed helical C-chain in 2-L(B), 2D layer of 2-D constructed by right-handed helical C-chains(C) and 2D layer of 2-L constructed by right-handed helical C-chains(D)

Fig.6 AB type double-layered framework of 2-D linked by hydrogen bonds(A), 3D supramolecular framework of 2-D(B) and the 4-connected sql net in 2-D(C)

Fig.7 PXRD patterns of complexes 1(A) and 2(B)(A) a. Simulated, 1-D, b. experimental, 1-D, c. experimental, 1-L; (B) a. simulated, 2-D, b. experimental, 2-D, c. experimental, 2-L.

Fig.8 TGA curves of complexes 1-D(a), 1-L(b)(A) and 2-D(a), 2-L(b)(B)

Fig.9 Solid-state CD spectra of bulk samples 1-D(a), 1-L(b)(A) and 2-D(a), 2-L(b)(B)

Fig.10 Fluorescent emission spectra of DPEE(a),(R)-H2CBA(b), 1-D(c) and 2-D(d) in the solid state at room temperature

References 40

[1]	Duarte M., Billing J., Yilmaz E.,J. Appl. Polym. Sci., 2016, DOI: 10.1002/APP.44104
[2]	Shen J., Okamoto Y., Chem. Rev., 2016, 116, 1094—1138
[3]	Fuchs I., Fechler N., Antonietti M., Mastai Y., Angew. Chem. Int. Ed., 2016, 55, 408—412
[4]	Li W., Wang B., Yang W., Deng J., Macromol. Rapid Commun., 2015, 36, 319—326
[5]	Zhang L., Qin L., Wang X. F., Cao H., Liu M. H., Adv. Mater., 2014, 26, 6959—6964
[6]	Kelly J. A., Giese M., Shopsowitz K. E., Maclachlan M. J., Acc. Chem. Res., 2014, 47, 1088—1096
[7]	Yoon M., Srirambalaji R., Kim K., Chem. Rev., 2012, 112, 1196—1231
[8]	Ma L., Abney C., Lin W. B., Chem. Soc. Rev., 2009, 38, 1248—1256
[9]	Xi X. B., Fang Y., Dong T. W., Cui Y., Angew. Chem., Int. Ed., 2011, 50, 1154—1158
[10]	Mo K., Yang Y. H., Cui Y., J. Am. Chem. Soc., 2014, 136, 1746—1749
[11]	Peng Y. W., Gong T. F., Cui Y., Chem. Commun., 2013, 49, 8253—8255
[12]	Liu Y., Xi X. B., Ye C. C., Gong T. F., Yang Z. W., Cui Y., Angew. Chem. Int. Ed., 2014, 53, 13821—13825
[13]	Wu P. Y., He C., Wang J., Peng X. J., Li X. Z., An Y. L., Duan C. Y., J. Am. Chem. Soc., 2012, 134, 14991—14999
[14]	Hang Q. X., He C., Zhao M., Qi B., Niu J. Y., Duan C. Y., J. Am. Chem. Soc., 2013, 135, 10186—10189
[15]	Han Q.X., Qi B., Ren W. M., He C., Niu J. Y., Duan C. Y.,Nat. Commun., 2016, DOI: 10.1038/ncomms10007
[16]	Kuang X., Ma Y., Su H., Zhang J., Dong Y. B., Tang B., Anal. Chem., 2014, 86, 1277—1281
[17]	Zhou C., Wen Y. H., Wu X. T., CrystEngComm., 2016, 18, 2792—2802
[18]	Wen H. R., Xie R. X., Liu S. J., Bao J., Wang F. F., Liu C. M., Liao J. S., RSC Adv., 2015, 5, 98097—98104
[19]	Bhunia A., Dey S., Moreno J. M., Diaz U., Concepcion P., Hecke K. V., Janiak C., Voort P. V. D., Chem. Commun., 2016, 52, 1401—1404
[20]	Ma L. Q., Lin W. B., J. Am. Chem. Soc., 2008, 130, 13834—13835
[21]	Chang C. L., Qi X. Y., Zhang J. W., Qiu Y. M., Li X. J., Wang X., Bai Y., Sun J. L., Liu H. W., Chem. Commun., 2015, 51, 3566—3569
[22]	Yuan S., Deng Y. K., Xuan W. M., Wang X. P., Wang S. N., Dou J. M., Sun D., Cryst. Eng. Comm,2014, 16, 3829—3833
[23]	Feng J. S., Ren M., Cai Z. S., Fan K., Bao S. S., Zheng L. M., Chem. Commun., 2016, 52, 6877—6880
[24]	Mihalcea I., Zill N., Mereacre V., Anson C. E., Powell A. K., Cryst. Growth Des., 2014, 14, 4729—4734
[25]	Sun J. W., Zhu J., Song H. F., Li G. M., Yao X., Yan P. F., Cryst. Growth Des., 2014, 14, 5356—5360
[26]	Jeong K. S., Go Y. B., Shin S. M., Lee S. J., Kim J., Yaghi O. M., Jeong N., Chem. Sci., 2011, 2, 877—882
[27]	Lun D. J., Waterhouse G. I. N., Telfer S. G., J. Am. Chem. Soc., 2011, 133, 5806—5809
[28]	Regati S., He Y., Thimmaiah M., Li P., Xiang S., Chen B., Zhao C. G., Chem. Commun., 2013, 49, 9836—9838
[29]	Zhao X., Wong M., Mao C., Trieu T. X., Zhang J., Feng P. Y., Bu X., J. Am. Chem. Soc., 2014, 136, 12572—12575
[30]	Kuang X., Ye S., Li X., Ma Y., Zhang C., Tang B., Chem. Commun., 2016, 52, 5432—5435
[31]	Yang X. L., Wu C. D., Cryst. Eng. Comm., 2014, 16, 4907—4918
[32]	Kumar N., Khullar S., Singh Y., Mandal S. K., Cryst. Eng. Comm., 2014, 16, 6730—6744
[33]	Chen L., Kang J., Cui H., Wang Y., Liu L., Zhang L., Su C. Y., Dalton Trans., 2015, 44, 12180—12188
[34]	Bisht K. K., Parmar B., Rachuri Y., Kathalikattil A. C., Suresh E., Cryst. Eng. Comm., 2015, 17, 5341—5356
[35]	Xu Z. X., Tan Y. X., Fu H. R., Liu J., Zhang J., Inorg. Chem., 2014, 53, 12199—12204
[36]	Xu X. Z., Tan Y. X., Fu H. R., Kan Y., Zhang J., Chem. Commun., 2015, 51, 2565—2568
[37]	Xu Z. Xu., Xiao Y., Kang Y., Zhang L., Zhang J., Cryst. Growth Des., 2015, 15, 4676—4686
[38]	Cui P., Chen Z., Gao D. L., Zhao B., Shi W., Cheng P., Cryst. Growth Des., 2010, 10, 4370—4378
[39]	Cui Y. J., Yue Y. F., Qian G. D., Chen B. L., Chem. Rev., 2012, 112, 1126—1162
[40]	Hu Z. C., Deiber B. J., Li J., Chem. Soc. Rev., 2014, 43, 5815—5840