Syntheses, Structures and Properties of Homochiral Metal-organic Frameworks with Helices and Trinuclear Cluster Units Based on Semirigid Proline Derivatives†

doi:10.7503/cjcu20180827

Abstract

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

CLC Number:

O614

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2019, 40(5): 873.

Figures/Tables 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)

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