具有三核Cd(Ⅱ)簇单元和螺旋链的脯氨酸类单一手性金属-有机框架材料的合成、 结构和性质

doi:10.7503/cjcu20180827

摘要/Abstract

摘要：

在溶剂热反应条件下, 使用含氮辅助配体1,4-二(4-吡啶基)苯(1,4-DPB)和半刚性脯氨酸衍生物配体(R)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(R)-H₃PIA]或(S)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(S)-H₃PIA]与Cd²⁺构筑了单一手性金属-有机框架材料[Cd_1.5((R)-PIA)(1,4-DPB)_1.5]·0.75H₂O·xGuest(1-D)和[Cd_1.5((S)-PIA)(1,4-DPB)_1.5]·0.75 H₂O·xGuest(1-L). 配合物1-D和1-L呈具有开放孔道的三维柱层式框架结构, 含有三核镉簇单元 Cd₃(CO₂)₆与两种螺旋链构建的波浪形Cd-PIA层. 分别对上述化合物进行了粉末X射线衍射、热重分析、圆二色谱和荧光光谱等测试. 测试结果显示配合物1-D和1-L都是以纯晶体的形式存在, 2种配合物的热失重曲线接近, 圆二色谱有明显的正负吸收峰, 符合其对映体的结构特征.

关键词: 单一手性, 脯氨酸衍生物, 金属-有机框架, 螺旋链, 镉簇

Abstract:

With the help of nitrogen heterocycle auxiliary ligand 1,4-di(pyridin-4-yl)benzene)(1,4-DPB), a pair of homochiral metal-organic frameworks named [Cd_1.5((R)-PIA)(1,4-DPB)_1.5]·0.75H₂O·xGuest(1-D) and [Cd_1.5((S)-PIA)(1,4-DPB)_1.5]·0.75 H₂O·xGuest(1-L)[H₃PIA=5-(2-carboxypyrrolidine-1-carbonyl)isophthalic acid] have been prepared from proline derivative ligands (R)-H₃PIA and (S)-H₃PIA and cadmium ions. Crystallographic analysis indicates that complexes 1-D and 1-L feature three-dimensional open pore structure, containing wavy metal-carboxylate layers and almost linear trinuclear cadmium cluster units. In complexes 1-D and 1-L, the wavy metal-carboxylate layers consists of two types of homochiral helical chains, which are constructed by PIA fragments and cadmium ions. Moreover, powder X-ray diffraction patterns(PXRD), thermogravimetric analysis(TGA), circular dichroism(CD) spectra, and photoluminescent spectra of complexes 1-D and 1-L were also investigated. The results show all the peak positions of simulated and experimental PXRD patterns match well with each other, indicating that the complexes were obtained as a single phase. Furthermore, TGA curves of complexes 1-D and 1-L are very similar to each other and their CD spectrum have obviously positive or negative signal, which accord with their enantiomeric properties.

Key words: Homochirality, Proline derivative, Metal-organic framework, Helical chain, Cadmium cluster

中图分类号:

O614

TrendMD:

徐中轩, 黄丽娜, 邓玉花, 蒙琴. 具有三核Cd(Ⅱ)簇单元和螺旋链的脯氨酸类单一手性金属-有机框架材料的合成、结构和性质. 高等学校化学学报, 2019, 40(5): 873.

XU Zhongxuan,HUANG Lina,DENG Yuhua,MENG Qin. Syntheses, Structures and Properties of Homochiral Metal-organic Frameworks with Helices and Trinuclear Cluster Units Based on Semirigid Proline Derivatives^†. Chem. J. Chinese Universities, 2019, 40(5): 873.

图/表 9

Fig.1 Structures of enantionpure ligands (R)-H3PIA and (S)-H3PIA and auxiliary N-donor linker 1,4-DPB

Table 1 Crystallographic parameters of complexes 1-D and 1-L

Complex	1-D	1-L
Empirical formula	C₃₈H₂₈Cd_1.5N₄O_7.75	C₃₈H₂₈Cd_1.5N₄O_7.75
Formula Mass	833.24	833.24
Crystal system	Orthorhombic	Orthorhombic
Space group	P2₁2₁2	P2₁2₁2
a/nm	1.57830(7)	1.57693(5)
b/nm	2.10476(12)	2.09224(7)
c/nm	1.60529(5)	1.60303(4)
α/(°)	90	90
β/(°)	90	90
γ/(°)	90	90
Unit cell volume/nm³	5.3327(4)	5.2889(3)
Temperature/K	293(2)	293(2)
Z	4	4
D_c/(g·cm^-3)	1.036	1.046
Radiation type	Mo Kα	Mo Kα
μ/mm^-1	0.642	0.647
F(000)	1672.0	1672.0
Reflections collected	59111	124047
Independent reflections(R_int)	14339(0.0707)	14975(0.0551)
R₁, wR₂[(I>2σ(I)]	0.0534, 0.1442	0.0476, 0.1302
R₁, wR₂(all data)	0.0658, 0.1497	0.0565, 0.1348
GOOF	1.056	1.098
Flack parameter	-0.010(14)	-0.020(8)
CCDC No.	1883497	1883499

Fig.2 Coordination environment of enantiomers 1-D(A) and 1-L(B) Symmetry codes: a. 0.5-x,-0.5+y,1-z; b. 0.5+x, 1.5-y,1-z; c. 0.5+x, 1.5-y, -z; d. 1-x, 2-y, z; e. -0.5-x, 0.5+y, 1-z; f. 0.5-x, 0.5+y, 1-z; g. x, y, -1+z.

Fig.3 The left-handed helical chain a in complex 1-D(A), the right-handed helical chain a in complex 1-L(B), the right-handed helical chain b in complex 1-D(C), the left-handed helical chain b in complex 1-D(D), the two-dimensional Cd-(R)-PIA layer of complex 1-D consisting of helical chains(E) and the two-dimensional Cd-(S)-PIA layer of complex 1-D consisting of helical chains(F)

Fig.4 1,4-DPB ligand simplied as a line(A), three-dimensional network of complex 1-D constructed by wavy Cd-(R)-PIA layers and 1,4-DPB ligands(B) and the tfz-d net of complex 1-D(C)

Fig.5 PXRD patterns(A) and TGA curves(B) of complexes 1-D and 1-L(A) a. Simulated 1-D, b. experimental 1-D, c. experimental 1-L; (B) a. complex 1-D, b. complex 1-L.

Fig.6 Solid state CD spectra of bulk samples 1-D(a) and 1-L(b)

Fig.7 UV-Vis absorption spectrum of complex 1-L

Fig.8 Fluorescent emission spectra of (S)-H3PIA(a) and complex 1-L(b)

参考文献 41

[1]	Ma L., Abney C., Lin W. B., Chem. Soc. Rev.,2009, 38, 1248—1256
[2]	Zhao M., Ou S., Wu C. D., Acc. Chem. Res.,2014, 47, 1199—1207
[3]	Zhang W., Xiong R. G., Chem. Rev.,2012, 112 , 1163—1195
[4]	Xia Q. C., Li Z. J., Tan C. X., Liu Y., Gong W., Cui Y., J. Am. Chem. Soc.,2017, 139, 8259—8266
[5]	Chen X., Jiang H., Hou B., Gong W., Liu Y., Cui Y., J. Am. Chem. Soc.,2017, 139, 13476—13482
[6]	Hou X. D., Xu T. T., Wang Y., Liu S. J., Chu R. R., Zhang J. X., Liu B., ACS Appl. Mater. Interfaces,2018, 10, 26365—26371
[7]	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
[8]	Yoon M., Srirambalaji R., Kim K., Chem. Rev.,2012, 112, 1196—1231
[9]	Slater B., Wang Z., Jiang S., Hill M. R., Ladewig B. P., J. Am. Chem. Soc.,2017, 139, 18322—18327
[10]	Tan C. X., Hang X., Li Z. J., Liu Y., Cui Y., J. Am. Chem. Soc.,2018, 140, 16229—16236
[11]	Gu Z. G., Zhang C. H., Zhang J., Bu X. H., Chem. Soc. Rev., 2016, 45, 3122—3144
[12]	Kuang X., Ma Y., Zhang C. Y., Su H., Zhang J., Tang B., Chem. Commun.,2015, 51, 5955—5958
[13]	Hang Q., He C., Zhao M., Qi B., Niu J., Duan C. Y., J. Am. Chem. Soc.,2013, 135, 10186—10189
[14]	Wen Y., Sheng T., Xue Z., Sun Z., Wang Y., Hu S., Huang Y., Li J., Wu X. T., Cryst. Growth Des.,2014, 14, 6230—6238
[15]	Ye H. T., Ren C.Y., Hou G. F., Yu Y. H., Xu. X., Gao J. S., Yan P. F., Ng S. W., Cryst. Growth Des.,2014, 14 , 3309—3318
[16]	Du X., Fan R., Wang X., Yu G., Qiang L., Wang P., Gao S., Yang Y. L., Cryst. Growth Des.,2016, 16, 1737—1745
[17]	Wu B. L., Wang S., Wang R., Xu J., Yuan D., Hou H., Cryst. Growth Des.,2013, 13, 518—525
[18]	Tanaka K., Sakuagi K., Ozaki H., Takada Y., Chem. Commun.,2018, 54, 6328—6331
[19]	Mande H. M., Ghalsasi P. S., Arulsamy N., Cryst. Growth Des.,2014, 14, 4254—4257
[20]	Song B. Q., Cheng D. Q., Ji Z., Tang J., Wang X. L., Zang H. Y., Su Z. M., Chem. Commun.,2017, 53, 1892—1895
[21]	An G., Yan P., Sun J., Li Y., Yao X., Li G. M., Cryst. Eng. Comm.,2015, 17, 4421—4433
[22]	Jiao C. Q., Zhao Z., Ma C., Sun Z. G., Dong D. P., Zhu Y. Y., Li J., Cryst. Growth Des.,2016, 16, 5624—5635
[23]	Gong C., Guo H., Zeng X., Xu H., Zeng Q., Zhang J., Xie J., Dalton Trans.,2018, 47, 6917—6923
[24]	Dubey M., Kumar A., Dhavale M. V., Kurungotc S., Panedy D. S., Cryst. Eng. Comm.,2015, 17, 8202—8206
[25]	Bisht K. K., Parmar B., Rachuri Y., Kathalikattil A. C., Suresh E., Cryst. Eng. Comm.,2015, 17, 5341—5356
[26]	Pejić J., Vu$\check{s}$ak D., Szalontai G., Prugove$\check{c}$ki B., Mrvo$\check{s}$-Sermek D., Matković-$\check{C}$alogović D., Sabolović J., Cryst. Growth Des.,2018, 18, 5138—5154
[27]	Wu X., Zhang H. B., Xu Z. X., Zhang J., Chem. Commun.,2015, 51, 16331—16333
[28]	Kundu T., Sahoo S. C., Saha S., Banerjee R., Chem. Commun.,2013, 49, 5262—5264
[29]	Burneo I., Stylianou K. C., Imaza I., Maspoch D., Chem. Commun.,2014, 50, 13829—13832
[30]	Strutt N. L., Zhang H., Stoddart J. F., Chem. Commun.,2014, 50, 7455—7458
[31]	Guan G. X., Liu X., Yue Q., Gao E. Q., Cryst. Growth Des.,2018, 18, 364—372
[32]	Xu Z. X., Tan Y. X., Fu H. R., Liu J., Zhang J., Inorg. Chem.,2014, 53, 12199—12204
[33]	Xu Z. X., Tan Y. X., Fu H. R., Kang Y., Zhang J., Chem. Commun.,2015, 51, 2565—2568
[34]	Xu Z. X., Fu H. R., Wu X., Kang Y., Zhang J., Chem. Eur. J.,2015, 21, 10236—10240
[35]	Xu Z. X., Wu X., Liu J., Kang Y., Zhang J., Cryst. Eng. Comm.,2015, 17, 6107—6109
[36]	Dolomanov O. V., Bourhis L. J., Gildea R. J., Howard J. A. K., Puschmann H., J. Appl. Cryst.,2009, 42, 339—341
[37]	Sheldrick G. M., Acta Cryst., 2015, A71, 3—8
[38]	Speck A. L., Acta Crystallogr., Sect. C: Struct. Chem., 2015, 71, 9—18
[39]	Aexandrov E. V., Blatov V. A., Kochetkov A. V., Proserpio D. M., Cryst. Eng. Comm.,2011, 13, 3947—3958
[40]	Sun Q., Lu J., Li J. L, Jiang L., Gu W., Liu X., Tian J. L., Yan S. P., Appl. Organomet. Chem.,2014, 28, 259—266
[41]	Hu Z. C., Deibert B. J., Li J., Chem. Soc. Rev.,2014, 43, 5815—5840