Homochiral Cluster-Organic Frameworks Constructed from

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Homochiral Cluster-Organic Frameworks Constructed from Enantiopure Lactate Derivatives Zhong-Xuan Xu, Yu Xiao, Yao Kang, Lei Zhang, and Jian Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b00958 • Publication Date (Web): 10 Aug 2015 Downloaded from http://pubs.acs.org on August 13, 2015

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Crystal Growth & Design

Homochiral Cluster-Organic Frameworks Constructed from Enantiopure Lactate Derivatives Zhong-Xuan Xu†,‡, Yu Xiao†, Yao Kang†, Lei Zhang†,* and Jian Zhang†,* †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, the Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China. ‡

Department of Chemistry, Zunyi Normal College, Zunyi, 563002, P. R. China

RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to) ABSTRACT: Two enantiopure organic linkers ((R)-H3CIA and (S)-H3CIA) derived from lactic acid have been synthesized and used to construct four pairs of homochiral metal−organic frameworks (HMOFs) with polymetallic building blocks. Crystallographic analysis indicates that H3CIA ligands can connect tetranuclear zinc units into kgd type layered structure, whilst the introduction of nitrogen heterocycle auxiliary ligands into this system gives rise to the formation of three-dimensional homochiral MOFs with different structural topologies. Physical characteristics of these complexes are also carried out, including thermal stabilities, solid-state circular dichroism (CD), and photoluminescent properties. Our results highlight the effective method to apply inexpensive and nontoxic chiral ligands to prepare interesting HMOFs.

Introduction Among different types of coordination polymers, homochiral metal−organic frameworks (HMOFs) have received extensive attention for their intriguing structures and diverse topologies as well as their potential applications in enantioselective processes, nonlinear optics and so on.1 Although enormous amounts of achiral coordination polymers with multiple application function have been reported in recent years,2 the design and

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construction of HMOFs still remains a great challenge.3 To obtain the HMOFs, in recent years, three general approaches have been developed: (1) use of enantiopure ligands, (2) chiral induction and (3) spontaneous resolution.4 Among them, the most effective method for the synthesis of HMOFs is to select an enantiopure organic ligand as the primary linker to impart homochirality to the frameworks.5 In contrast, it is difficult to construct HMOFs from achiral or racemic ligands, because the spontaneous resolution phenomena is very rare and only occurs occasionally. Therefore, the design and synthesis of new enantiopure ligands is the key point for the rational construction of HMOFs.6 Lactic acid, which is readily available, inexpensive and nontoxic, may be an ideal chiral ligand for the construction of HMOFs.7 However, due to its structure flexibility, lactic acid based HMOFs with stable architecture are still limited. In order to overcome this defect, it is necessary to modify the functional groups (-OH or –COOH) of lactic acid with rigid aromatic parts.8 Inspired by this methodology, we try to modify the dimethyl 5-hydroxyisophthalate ligand into a chiral linker via attaching one lactic acid group. It has already been well established that isophthalate-type ligands are very powerful in the construction of MOFs.9 Therefore, such a combination of isophthalate and chiral lactic acid functionalities will provide a new and feasible approach to design and prepare diverse HMOFs with potential applications. Furthermore, to increase the structural dimensions of HMOFs, the introduction of auxiliary N-donor ligands into the metal−chiral carboxylate systems would be an effective method. According to the above mentioned synthetic strategy, a pair of enantiopure 5-(1-carboxyethoxy)isophthalic acid (denoted: (R)-H3CIA and (S)-H3CIA) (Scheme 1) have been successfully synthesized. Moreover, by the application of this pair of enantiopure ligands,

four

pairs

of

enantiomeric

HMOFs,

namely

[Zn4((R)-CIA)2(OH)2

(H2O)4]⋅3.5H2O(1-D), [Zn4((S)-CIA)2(OH)2(H2O)4]⋅3.5H2O (1-L), [Cd3((R)-CIA)2(dpe)2]⋅ 0.5H2O (2-D), [Cd3((S)-CIA)2(dpe)2]⋅0.5H2O (2-L), [Cd3((R)-CIA)2(tmdpy)2]⋅H2O (3-D), [Cd3((S)-CIA)2(tmdpy)2]⋅H2O

(3-L),

[Cd4((R)-CIA)2(OH)2(1.4-DIB)2]⋅4.5H2O

(4-D),

[Cd4((S)-CIA)2(OH)2(1.4-DIB)2]⋅4.5H2O (4-L) (Table 1) have been hydrothermally prepared. In this contribution, we report their synthesis, crystal structures, thermal stabilities, CD spectra and luminescent properties. Experimental Section


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General Procedures. All the chemical reagents used in reactions were purchased from Energy-Chemical and Sigma-Aldrich and used without further purification. 1H NMR (400 MHz) and

13

C NMR

(100 MHz) spectra were recorded in DMSO (δ 2.49) or CDCl3 (δ 7.26) solutions using a Burker AVANCE 400 spectrometer. Chemical shifts are reported as δ values in parts per million (ppm) relative to tetramethylsilane (TMS) for all recorded NMR spectra. The Mass spectra and elemental analysis were carried out by the analysis center of our institute. FT-IR spectra were measured as KBr pellets on a Nicolet Magna 750 FT-IR spectrometer in the range of 400-4000cm-1. Thermal stability studies were performed on a NETSCHZ STA-449C thermoanalyzer with a heating rate of 10°C/min from 30℃ to 800℃ in N2. All Powder X-ray diffraction (PXRD) analysis were recorded on a Miniflex(Ⅱ) diffractometer with Cu-Kαradiation (λ = 1.54056 Å) in a range of 5.00−50.00°. Luminescence spectra were recorded on a Shimadzu RF-5301 spectrophotometer. The solid CD spectra were measured on a MOS-450 spectropolarimeter using KCl pellets.

Scheme 1. Synthetic routes to the ligands (R)-H3CIA and (S)-H3CIA and structures of three auxiliary N-donor ligands.

Synthesis of dimethyl-5-((1-methoxy-1-oxopropan-2-yl)oxy)isophthalate (3a and 3b ): To a solution of dimethyl 5-hydroxyisophthalate (1, 4.2g, MW =210.2, 0.02 mol), L-(–)-lactic acid methyl ester ((S)-methyl lactate) or D-(–)-lactic acid methyl ester ((R)-methyl lactate, 2,



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2.2g, MW = 104.1, 0.021mol) and triphenylphosphine (PPh3, 5.8g, MW = 262.3, 0.022mol) in dry tetrahydrofuran (THF, 50mL), diethyl diazocarboxylate (DEAD) solution (0.022mol in 10mL THF) was dropwisely added over 10min at 0°C. After stirring for 2h at the same temperature, the reaction mixture was concentrated. Then the residue was purified by flash column chromatography on silica gel eluting with 20% ethyl acetate in petroleum ether to give 3 (4.44g, MW = 296.3, 0.015mol, 75%, >96% ee) as a white solid. The enantiomeric excess was determined by HPLC analysis with a chiral HPLC column (DAICEL CHIRALCEL AD-H, 10.0% 2-propanol in hexane, 1.0mL/min). The retention time corresponding to 3 and its enantiomer was 9.4 and 6.9 min, respectively. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.32-8.31 (1H, d, J = 1.3Hz), 7.75 (2H, s), 4.93-4.8 (1H, q, J = 2.8Hz), 3.94 (6H, s), 3.78 (3H, s), 1.68-1.67 (3H, d, J = 2.8Hz); 13C NMR (100 MHz, CDCl3),δ(ppm): 171.78, 165.88, 157.65, 131.96, 123.86, 120.47, 72.83, 52.44, 52.42, 18.38; LRSM (ESI): Mass calcd for C14H16O7 [M+H]+, 297.2; found 297.2. Synthesis of 5-(1-carboxyethoxy)isophthalic acid (4a and 4b): dimethyl 5-((1-methoxy1-oxopropan-2-yl)oxy)isophthalate (3a or 3b, 5.93g, MW = 296.3, 0.02mol), methanol (10 mL), water (40 mL) and solid sodium hydroxide (1.8g, 45mmol) were added to a 100 mL round-bottomed flask containing a stirring bar. The reaction mixture was stirred and heated at 50℃ for 10h, and then the result solution was acidified to pH 1-2 with concentrated aqueous HCl in an ice bath. The precipitated solid was separated by filtration to give pure compound 4a or 4b (4.32g, MW = 254.2, 0.017mol, 85%) as a white solid: 1H NMR (400 MHz, DMSO), δ(ppm): 13.306 (3H, brs), 8.08 (1H, m), 7.587-7.589 (2H, d, J = 0.8Hz ), 4.97-5.02 (1H, q, J = 2.8Hz ), 1.53- 1.55 (3H, d, J = 6.8Hz); 13C NMR (100 MHz, DMSO), δ(ppm): 173.15, 166.72.54, 167.06, 158.12, 133.05, 123.07, 119.90, 72.52, 18.65; LRSM(ESI): Mass calcd for C11H10O7 [M+H]+, 253.2; found 253.2. Synthesis of [Zn4((R)-CIA)2(OH)2(H2O)4]⋅3.5H2O (1-D): Zn(NO3)2·6H2O (0.2mmol, 60mg), (R)-H3CIA (0.1mmol, 26mg), Na2CO3 (0.15mmol, 16mg), and distilled water (4mL) were mixed in a 23-mL teflon cup, and the mixture was stirred for 5 min. After the vessel was sealed and heated at 120℃ for 72 hours, the autoclave was subsequently allowed to cool to room temperature. Colorless crystals (32mg, 68%, based on (R)-H3PIA) were obtained after filtration. Elemental analysis (%) calcd for 1-D (Zn8C44H62O47): C 28.32, H 3.35; found:


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C 29.12, H 3.58. IR (solid KBr pellet, cm-1): 3354.8m, 1619.7s, 1572.3s, 1452.7s, 1421.7s, 1380.5s, 1094.3m, 1115.0w, 1094.8w, 979.9w, 782.7m, 725.3m. Synthesis of [Zn4((S)-CIA)2(OH)2(H2O)4]⋅3.5H2O (1-L): The same procedure as 1-D, except (S)-H3CIA was used. Colorless crystals (26mg, 55%, based on (S)-H3CIA) were obtained after filtration. Elemental analysis (%) calcd for 2 (Zn8C44H62O47): C 28.32, H 3.35; found: C 29.32, H 3.67. IR (solid KBr pellet, cm-1): 3354.8m, 1624.3s, 1567.7s, 1452.7s, 1427.1s, 1375.1, 1250.1m, 1120.5w, 1084.0w, 1068.4w, 979.9w, 782.7w, 720.6w. Synthesis of [Cd3((R)-CIA)2(dpe)2]⋅0.5H2O (2-D): Cd(NO3)2·4H2O (0.2mmol, 62mg), (R)-H3CIA (0.1mmol, 26mg), Na2CO3 (0.15mmol, 16mg), dpe (0.15mmol, 27mg), and distilled water (4mL) were mixed in a 23-mL teflon cup, and the mixture was stirred for 5 min. After the vessel was sealed and heated at 120℃ for 72 hours, the autoclave was subsequently allowed to cool to room temperature. Colorless crystals (24mg, 40%, based on (R)-H3CIA) were obtained after filtration. Elemental analysis (%) calcd for 2-D (Cd6C92H70O29N4): C 46.62, H 2.98, N 2.36; found: C 47.21, H 3.15, N 2.52. IR (solid KBr pellet, cm-1): 3467.0m, 3038.1w, 1603.4s, 1556.8s, 1442.7m, 1390.6s, 1261.0m, 1084.0w, 1011.0w, 834.8m, 782.7m, 725.3m, 549.0m. Synthesis of [Cd3((S)-CIA)2(dpe)2]⋅0.5H2O (2-L): The same procedure as 2-D, except (S)-H3CIA was used. Colorless crystals (30mg, 50%, based on (S)-H3CIA) were obtained after filtration. Elemental analysis (%) calcd for 2-L (Cd6C92H70O29N4): C 46.62, H 2.98, N 2.36; found: C 47.31, H 3.45, N 2.22. IR (solid KBr pellet, cm-1): 3462.0m, 3042.0w, 1604.1s, 1558.3s, 1447.3m, 1386.8s, 1264.9m, 1087.9w, 1011.8w, 840.2m, 774.2m, 723.7m, 561.5m. Synthesis of [Cd3((R)-CIA)2(tmdpy)2]⋅H2O (3-D): Cd(NO3)2·4H2O (0.2mmol, 62mg), (R)-H3CIA (0.1mmol, 26mg), Na2CO3 (0.15mmol, 16mg), tmdpy (0.15mmol, 30mg), and distilled water (4mL) were mixed in a 23-mL teflon cup, and the mixture was stirred for 5 min. After the vessel was sealed and heated at 160℃ for 48 hours, the autoclave was subsequently allowed to cool to room temperature. Colorless crystals (44mg, 70%, based on (R)-H3CIA) were obtained after filtration. Elemental analysis (%) calcd for 3-D (Cd3C48H44O15N4): C 45.97, H 3.54, N 4.47; found: C 44.85, H 3.24, N 4.21. IR (solid KBr pellet, cm-1): 3437.9m, 3069.1w, 2928.6w, 2866.5w, 1608.8s, 1552.1s, 1365.0s, 1255.6m, 1130.6w, 1084.0w, 1011.0w, 856.7w, 819.2w, 777.3m, 720.6m, 574.7w.



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Synthesis of [Cd3((S)-CIA)2(tmdpy)2]⋅H2O (3-L): The same procedure as 3-D, except (S)-H3CIA was used. Colorless crystals (41mg, 65%, based on (S)-H3CIA) were obtained after filtration. Elemental analysis (%) calcd for 3-L (Cd3C48H44O15N4): C 45.97, H 3.54, N 4.47; found: C 44.85, H 3.24, N 4.21. IR (solid KBr pellet, cm-1): 3432.5m, 3063.7w, 2918.5w, 2861.1w, 1603.4s, 1552.1s, 1366.0s, 1265.6m, 1125.9w, 1089.4m, 1021.9m, 860.4m, 819.2m, 788.2m, 720.6m, 580.1w. Synthesis of [Cd4((R)-CIA)2(OH)2(1.4-DIB)2]⋅4.5H2O (4-D): Cd(NO3)2·4H2O (0.2mmol, 62mg), (R)-H3CIA (0.1mmol, 26mg), Na2CO3 (0.15mmol, 16mg), 1.4-DIB (0.15mmol, 32mg), and distilled water (4mL) were mixed in a 23-mL teflon cup, and the mixture was stirred for 5 min. After the vessel was sealed and heated at 140℃ for 48 hours, the autoclave was subsequently allowed to cool to room temperature. Colorless crystals (33mg, 43%, based on (R)-H3CIA) were obtained after filtration. Elemental analysis (%) calcd for 4-D (Cd4C46H45N8O20.50): C 37.14, H 3.05, N 7.53; found: C 37.72, H 2.84, N 7.41. IR (solid KBr pellet, cm-1): 3661.5w, 3354.8m, 3125.8m, 1624.3s, 1562.4s, 1525.7s, 1400.7s, 1365.0s, 1313.0m, 1230.0m, 1110.4w, 1073.9m, 844.9m, 819.2m, 792.8m, 715.2m, 657.3m, 543.6w. Synthesis of [Cd4((R)-CIA)2(OH)2(1.4-DIB)2]⋅4.5H2O (4-L): The same procedure as 4-D, except (S)-H3CIA was used. Colorless crystals (37mg, 50%, based on (S)-H3CIA) were obtained after filtration. Elemental analysis (%) calcd for 4-L (Cd4C46H45N8O20.50): C 37.14, H 3.05, N 7.53; found: C 37.48, H 3.24, N 7.32. IR (solid KBr pellet, cm-1): 3666.9w, 3349.4m, 3121.2m, 2975.2w, 1629.8s, 1567.7s, 1515.6s, 1406.2s, 1369.7s, 1302.1m, 1245.5m, 1115.0w, 1068.4m, 819.2w, 798.3w, 772.7w, 709.8w, 653.1w, 549.1. X-ray Crystallographic analysis. The diffraction data for the compounds were collected on a SuperNova or Oxford diffractometer. The structures were solved by direct methods and refined on F2 full-matrix least-squares using the SHELXTL-97 program package.10 Some disordered atoms, such as C14 in complex 1-D, C3 in complex 1-L, C1, C3 in complex 2-L, C3, O2, O1, O1W in complex 3-D, and C3, O2, O1W in complex 3-L have been refined isotropically. In addition, all isolated O atoms have been considered as water atoms. Crystal data for the compounds were summarized in Table 1.

Table 1. Crystallographic Data and Structure Refinement for Compounds 1−4


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Compound reference

1-D

1-L

2-D

2-L

Chemical formula

C22H29O23.50Zn4

C22H29O23.50Zn4

C46H35Cd3N4O14.50

C46H35Cd3N4O14.50

Formula Mass

930.93

930.93

1212.98

1212.98

Crystal system

Monoclinic

Monoclinic

Monoclinic

Monoclinic

a/Å

7.5555(2)

7.5428(2)

9.4464(3)

9.4565(10)

b/Å

18.9892(4)

18.9688(5)

26.2464(8)

26.2364(18)

c/Å

11.4893(3)

11.5038(4)

9.7686(3)

9.7671(10)

α/°

90.00

90.00

90.00

90.00

β/°

99.658(3)

99.632(3)

117.108(4)

117.169(14)

90.00

90.00

90.00

90.00

Unit cell volume/Å

1625.04(7)

1622.74(8)

2155.91(12)

2155.9(4)

Temperature/K

293(2)

293(2)

293(2)

293(2)

Space group

P2(1)

P2(1)

P2(1)

P2(1)

Z

2

2

2

2

Radiation type

MoKα

MoKα

MoKα

CuKα

Reflections/unique

11488/5417

6351/4984

8196/4951

7881/5700

Rint

0.0245

0.0217

0.0363

0.0352

R1,wR2 (I > 2σ(I))

0.0354, 0.1142

0.0381, 0.1195

0.0324, 0.0857

0.0411, 0.1061

0.0377, 0.1165

0.0416, 0.1234

0.0365, 0.0875

0.0439, 0.1084

Goodness of fit on F

1.015

0.989

1.067

1.003

Compound reference

3-D

3-L

4-D

4-L

Chemical formula

C24H22Cd1.50N2O7.50

C24H22Cd1.50N2O7.50

C46H45Cd4N8O20.50

C46H45Cd4N8O20.50

Formula Mass

627.04

627.04

1487.50

1487.50

γ/° 3

R1,wR2 (all data) 2

Crystal system

Trigonal

Trigonal

Monoclinic

Monoclinic

a/Å

9.9455(3)

9.9361(2)

11.3022(5)

11.3063(7)

b/Å

9.9455(3)

9.9361(2)

20.8207(5)

20.8442(9)

c/Å

42.2668(18)

42.3479(18)

12.2420(6)

12.2438(9)

α/°

90.00

90.00

90.00

90.00

β/°

90.00

90.00

116.513(5)

116.542(9)

γ/°

120.00

120.00

90.00

90.00

Unit cell volume/Å3

3620.6(2)

3620.71(19)

2577.82(18)

2581.4(3)

Temperature/K

293(2)

293(2)

293(2)

295.93(10)

Space group

P3(2)21

P3(1)21

P2(1)

P2(1)

Z

6

6

2

2

Radiation type

MoKα

MoKα

MoKα

CuKα

Reflections/unique

7530/4236

7240/4006

17734/8976

10363/7608

Rint

0.0378

0.0302

0.0357

0.0394

R1,wR2 (I > 2σ(I))

0.0604/0.1605

0.0593/0.1811

0.0309/0.0728

0.0459/0.1231

R1,wR2 (all data)

0.0667/0.1658

0.0628/0.1867

0.0360/0.0757

0.0495/0.1266

Goodness of fit on F2

1.099

1.071

1.012

0.991

Flack parameter

-0.01(7)

0.03(8)

-0.01(2)

0.002(9)

Results and Discussion



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Despite hydrothermal reaction in a “black box” and being somewhat complicated, it has been proven to be an effective method in preparing HMOFs. Herein, four pairs of HMOFs were successfully prepared by hydrothermal reactions at 120−160°C. Compounds 1-D and 1-L show 2D architecture with tetranuclear units, whereas compounds 2−4 exhibit 3D pillared-layer structures with trinuclear or tetranuclear units in the presence of different N donor co-ligands. Furthermore, all HMOFs are very stable in air and insoluble in water and common organic solvents. Considering that compounds 1-D and 1-L, 2-D and 2-L, 3-D and 3-L, and 4-D and 4-L are enantiomers, only the structural details of 1-D, 2-D, 3-D and 4-D are described below as representatives.

Figure 1. Schematic illustrations of the structure of 1-D: (a) the different coordination modes of (R)-CIA3− ligands in 1-D; (b) tetranuclear Zn-cluster substructure; (c) 2D framework of 1-D; and (d) kgd topological net.

Structure of [Zn4((R)-CIA)2(OH)2(H2O)4]⋅3.5H2O (1-D) and [Zn4((S)-CIA)2(OH)2(H2O)4] ⋅3.5H2O (1-L): Single-crystal X-ray (XRD) study reveals the compound 1-D is an interesting 2D HMOF and crystallizes in the chiral space group P21 with a Flack parameter of -0.013(14). There are two deprotonated (R)-CIA3- ligands, four independent Zn(II) ions, two µ3-OH groups, four coordinated water molecules and three and a half lattice water molecules in the asymmetric unit of 1-D. The coordination modes of (R)-CIA3- ligand are shown in Figure 1a and each (R)-CIA ligand is a κ7-linker and connects six Zn(II) ions. It is notable that four independent Zn(II) ions form a tetranuclear unit [Zn4(µ3-OH)2]6+ in inerratic parallelogram type in the same plane through bonding from two bridging µ3-OH, six


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carboxylates and two ether oxygen groups of (R)-CIA ligands (Figure 1b). In the tetrameric unit, all Zn(II) ions display distorted coordination octahedral geometry: Zn(1) and Zn(4) are coordinated to four bridging carboxylates, one ether oxygen, one bridging µ3-OH and one water; Zn(2) and Zn(3) are coordinated to three bridging carboxylates, two bridging µ3-OH and one water. Each tetranuclear unit is linked by six (R)-CIA3- ligands to form a 2D framework (Figure 1c). From the viewpoint of structural topology, the (R)-CIA ligands and the tetrameric units can be viewed as the 3- and 6-connected nodes, respectively. Thus, the whole framework of 1-D can be can be described as a (3, 6)-connected kgd net with point (Schläfli) symbol of (43)2(46.66.83) (Figure 1d).

Figure 2. (a) The different coordination modes of (R)-CIA3- ligands in 2-D; (b) trinuclear Cd-cluster substructure and coordination modes of dpe ligands in 2-D; (c) 2D Cd-(R)-CIA layer in 2-D; and (d) topological net of the Cd-(R)-CIA layer in 2-D.

Structures of [Cd3((R)-CIA)2(dpe)2]⋅0.5H2O (2-D) and [Cd3((S)-CIA)2(dpe)2]⋅0.5H2O (2-L): Compounds 2-D and 2-L also crystallize in the monoclinic space group P21 with Flack parameters of -0.04(4) and 0.001(10), respectively, indicating the enantiomeric purity of the single crystals. The asymmetric unit in 2-D is composed of three independent Cd(II) ions, two (R)-CIA ligands, two dpe ligands and half an uncoordinated H2O molecule. The (R)-CIA ligand acts as a κ7-linker and connects six Cd(II) ions (Figure 2a). For the unique coordination modes of (R)-CIA3- ligand, a linear trinuclear Cd (Cd1, Cd2, Cd3) unit



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Cd3(CO2)6 is formed (Figure 2b). In this Cd3(CO2)6 unit, Cd1 and Cd3 have distorted pentagonal bipyramid geometries, which are both coordinated by five carboxylate O atoms from three (R)-CIA ligands, two N atoms from two dpe ligands. Cd2 shows distorted trigonal bipyramid geometry, and it is coordinated by six O atoms from six carboxylate groups. If only the connectivity between (R)-CIA3- and Cd3(CO2)6 unit is considered, a 2D Cd-(R)-CIA layer is generated (Figure 2c). This Cd-(R)-CIA layer can be reduced into a kgd net, which is similar to 1-D (Figure 2d). Each Cd-(R)-CIA layer is further pillared by dpe ligand resulting in a 3D pillared-layer framework (Figure 3e).

Figure 3. (a) The left-handed three-stranded helical channel in 2-D; (b) the right-handed three-stranded helical channel in 2-L; (c) the right-handed three-stranded helical channel in 2-D; (d) the left-handed three-stranded helical channel in 2-L; (e) the 3D framework of 2-D consisting of three-stranded left-handed helical channel and right-handed channel; (f) the 3D framework of 2-L consisting of three-stranded helical right-handed channel and left-handed channel.

The outstanding structural feature of 2-D (2-L) is the presence of two types of 1D narrow helical channels: left-handed channel and right-handed channel, as dictated by the chirality of the CIA ligands (Figure 3). As depicted in Figure 3a, in 2-D the Cd(II) ions are coordinated


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by dpe and the isophthalate unit from (R)-CIA3- ligand to form an infinite left-handed helical chain running along the a-axis, and it is the opposite phenomenon (homo right-handed helical chains) in 2-L (Figure 3b). In 2-D, the left-handed channel is formed by three corresponding left-handed chains, which is also constructed by Cd(II) ions, dpe ligand and carboxylate groups of PIA fragment (Figure 2c). In same way, the opposite phenomenon exists in 2-L (Figure 3d). Finally, each helical channel is further linked to two adjacent opposite channels (Figure 2e and 2f) to construct the 3D framework of 2-D or 2-L. All the helical channels are generated around the crystallographic 21 screw axis, which is the mark of P21 space group. By considering (R)-CIA (or (S)-CIA) ligands as 3-connected nodes and Cd3(CO2)6 units as 10-connected nodes, the whole framework of 2-D (or 2-L) can be described as (3,10) connected topology with point (Schläfli) symbol of (410·632·83)(43)2 (Figure S9).

Figure 4. (a) The coordination environment of the Cd-cluster and coordination modes of tmdpy ligand in 3-D; (b) 2D Cd-(R)-CIA layer in 3-D; and (c) topological kgd net of the Cd-(R)-CIA layer.

Structures of [Cd3((R)-CIA)2(tmdpy)2]⋅H2O (3-D) and [Cd3((S)-CIA)2(tmdpy)2]⋅H2O (3-L): X-ray determination has revealed that compounds 3-D and 3-L crystallize in chiral trigonal P3221 and P3121 space groups with Flack parameters of -0.01(7) and 0.03(8), respectively, which are different from those of compounds 1-D(1-L) and 2-D(2-L). The asymmetric unit of 3-D contains one and a half Cd2+ centers, one deprotonated (R)-PIA3−



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ligand, one tmdpy ligand and one half lattice water molecule. Similar to the compound 2-D, (R)-CIA ligand in 3-D also acts a κ8-linker and connects six Cd(II) ions (Figure 4a). Cd1 has an octahedral coordination geometry and is coordinated by six oxygen atoms from six carboxylate groups of six (R)-CIA ligands, while Cd2 is surrounded by five oxygen atoms from three carboxylate groups of three (R)-CIA ligands and two nitrogen atoms from two tmdpy ligands to show a distorted pentagonal bipyramid geometry. In 3-D, there is a linear trinuclear Cd (Cd2, Cd1, Cd2a) unit Cd3(CO2)6 which is surrounded by four pyridine groups and six carboxylate groups. Furthermore, a 2D Cd-(R)-CIA layer with kgd net also exists in 3-D (Figure 4b,c) and is further pillared by tmdpy generating a 3D framework (Figure 5e).

Figure 5. Schematic illustrations of 3-D and 3-L: (a) the small left-handed double-stranded helical chain in 3-D; (b) the small right-handed double-stranded helical chain in 3-L; (c) the large right-handed three-stranded helical chian in 3-D; (d) the large left-handed three-stranded helical chain in 3-L; (e) the 3D framework of 3-D consisting of small helical chain and large helical chain; (f) the 3D framework of 3-L consisting of small helical chain and large helical chain.

The outstanding structural feature of 3-D is also the presence of two types of helical chains (Fig. 5). As shown in Figure 5a, the Cd2 is bridged by two nitrogen atoms from two tmdpy ligands to form an infinite small left-handed double-stranded helical chain along to b-axis, and the opposite phenomenon (right-handed helical chain) exists in 3-L (Fig. 5b). As a secondary building unit, each small helical chain is further linked to two adjacent large


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helical chains (Figure 5e and 5f). The large right-handed three-stranded helical chain in 3-D (or left-handed helical chain in 3-L) contains four Cd2 ions, two tmdpy ligands and two (R)-CIA (or (S)-CIA) fragments per turn (Figure 5c and 5d). It should be noted that large helical chain forms an irregular right-handed helical channels in 3-D (left-handed helical channel in 3-L). From the viewpoint of structural topology, CIA3- ligands are three-connected nodes, trinuclear Cd units can be considered as 10-connected nodes, and tmdpy ligands are simply viewed as linkers. Therefore, the whole 3D frameworks of 3-D (3-L) should be simplified as a (3,10)-connected net with a point symbol of (43)2(46.637.82) (Figure S10).

Figure 6. (a) The different coordination modes of (R)-CIA3- ligand in 4-D; (b) tetranuclear metal cluster substructure and coordination modes of 1.4-DIB ligand; (c) 2D Cd-(R)-CIA layer in 4-D; and (d) topological net of the Cd-(R)-CIA layer; (e) the 3D pillared-layer framework of 4-D; (f) 3,10-connected 3D net of compound 4-D.

Structures of [Cd4((R)-CIA)2(OH)2(1.4-DIB)2]⋅4.5H2O (4-D) and [Cd4((S)-CIA)2(OH)2 (1.4-DIB)2]⋅4.5H2O (4-L): Compounds 4-D and 4-L crystallize in monoclinic chiral space group P21 with Flack parameters of -0.01(2) and 0.002(9), respectively. The asymmetric units



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of 4-D is composed of four independent Cd atoms, two (R)-CIA3- ligands, two µ3-OH groups, two 1.4-DIB ligands and four and a half lattice water molecules. Just like the compound 1-D, each (R)-CIA3- ligand in 4-D acts as κ7-linker to link six Cd(II) ions through its three carboxylate groups and an ether oxygen group (Figure 6a). In the tetrameric subunit, Cd4 and Cd3 adopt an octahedral geometry and are coordinated by three oxygen atoms from three carboxylate groups from three (R)-CIA3- ligand, two bridging µ3-OH groups and a nitrogen atom from a 1.4-DIB ligand, respectively, whereas Cd1 and Cd2 have a distorted octahedral geometry and coordinate with four oxygen atoms from three carboxylate groups from three (R)-CIA3- anion and a ether oxygen group, a bridging µ3-OH group and a nitrogen atom from a 1.4-DIB ligand (Figure 6b). The tetrameric subunits are connected by six carboxylate groups from six (R)-CIA3- ligands to form into a 2D Cd-(R)-CIA layer with kgd net along bc plane (Figure 6c and 6d). Consequently, the adjacent Cd-(R)-CIA layers are further linked to 3D pillared-layer network by 1.4-DIB ligands (Figure 6e). In the same way as 2-D and 3-D, (R)-CIA3- ligands in 4-D are still simplifed as three-connected nodes, tetrameric Cd-subunits are seen as 10-connected nodes and 1.4-DIB ligands are only linkers. As a result, the whole 3D pillared-layer framework of 4-D is topologically represented as a (3,10)-connected net with a point symbol of (410.633.82)(43)2 (Figure 6f) .

Discussion According to the above structural description of four pairs of HMOFs, we find that (R)-CIA3- and (S)-CIA3- ligands can adopt various coordination modes and they are a pair of good candidates to construct interesting HMOFs. As result of the unique coordination modes of the chiral CIA ligands, all of the eight complexes have a Zn-CIA or Cd-CIA layer with (3, 6)-connected kgd net. Tetrametalic Zn-clusters or Cd-clusters in complexes 1-D, 1-L, 4-D and 4-L are inerratic parallelogram type, while trimetallic Cd-clusters in complexes 2-D, 2-L, 3-D and 3-L are linear. Furthermore, the helices induced phenomenon from chiral ligands can be found in the frameworks of 2-D, 2-L, 3-D and 3-L. Finally, the different structures of the chiral compounds 2-4 with the same chiral (R)-CIA3- ((S)-CIA3-) ligand and the same Cd2+ center indicate that the N donor auxiliary ligands have a great influence on the structures of the HMOFs for their different structures.


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PXRD Patterns and Thermal Analysis. Powder X-ray diffraction (PXRD) experiments have been used to check the phase purity of complexes 1-4. As shown in the Figure S11-S14, all the peak positions displayed in the measured patterns are in good agreement with those in the simulated patterns generated from single-crystal diffraction data, indicating that all the crystal structures are truly representative of the bulk crystal products. Furthermore, some differences in intensity may be owing to the preferred orientation of the powder samples. To investigate the thermal stabilities of these HMOFs, the thermal behaviors of 1−4 have been tested from room temperature to 800°C under a nitrogen atmosphere (Figure S15-18), showing that these four pairs of HMOFs are all quite stable. The frameworks of 1-D and 1-L display the first weight loss of 6.72% (calucated, 6.78%) from 30 to 250°C and begin to collapse above 350°C. In the case of complexes 2-D and 2-L, no obvious weight loss took place until the temperature reached 420°C, where the frameworks of 2-D and 2-L began to collapse. The TG curves of 3-D and 3-L indicate that the frameworks of these two complexes are stable up to 250°C. For complexes 4-D and 4-L, gradual weight losses between 30 and 150°C are attributed to the release of lattice water molecules (observed, 5.13%; calculated, 5.45%), and the anhydrous frameworks began to decompose from 370°C.

Figure 7. The solid-state CD spectra of 1-D and 1-L (a), 2-D and 2-L (b), 3-D and 3-L(c) and 4-D and 4-L (d).

Circular Dichroism and Second-Harmonic Generation Efficency. Considering that all



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the complexes in this contribution crystallize in chiral space groups, their solid-state circular dichroism (CD) measurements have been performed to further demonstrate the homochirality of theirs (Figure 7). The CD spectrum of complex 1-D exhibits an obvious positive CD signal at 335 nm, while complex 1-L displays a negative CD signal at 335 nm. As shown in Figure 7b , the CD spectrum of complex 2-D has a positive Cotton effect with peak at 375 nm and 290nm, but complex 2-L exhibits a negative positive Cotton effect at 375nm and 275nm. Furthermore, complex 3-D shows a positive CD signal at 360 nm and a negative CD signal at around 330 nm and 3-L has the opposite CD signal at 360 nm and 325 nm (Figure 7c). The CD spectrum for the bulk sample of 4-D exhibits a positive Cotton effect with peak at 360 nm and a negative Cotton effect 325nm. Meanwhile, a mirror image is observed for 4-L. In a word, 1-L and 1-D, 2-D and 2-L, 3-D and 3-L, and 4-D and 4-L have been confirmed to be enantiomers, respectively. 1-D(1-L), 2-D(2-L), 3-D(3-L) and 4-D(4-L) are all chiral complexes with noncentrosymmetric crystal structures, so their second-order NLO properties have been carried out by the Kurtz–Perry method at room temperature. Preliminary experimental results show that 1-D, 2-D, 3-D and 4-D are SHG-active with efficiencies approximately 0.5, 0.3, 0.4 and 0.25 times that of KDP, respectively, which may have potential application as nonlinear optical (NLO)-active materials.

Figure 8. Fluorescent emission spectra of complexes 1−4

Photochemical Properties. The photoluminescent properties of d10 metal coordination


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compounds have been attracting more interest for their potential applications as fluorescence-emitting materials. Therefore, in this work, the solid-state excitation and emission spectra for complexes 1-4 were studied in the solid state at room temperature (Figure 8). The emission spectra have peaks with maxima at 402 nm (λex =325 nm) for 1-D, 377 nm (λex =336 nm) for 2-D, 427 nm (λex =337 nm) for 3-D, and 437 nm (λex =371 nm) for 4-D, respectively. In order to understand the nature of above emission bands, the luminescence properties of the H3CIA ligand, dpe ligand and tmdpy ligand have been also measured (Figure S19). Compared to these emission peaks of H3CIA ligand, dpe ligand and tmdpy ligand, the emissions of 1-D, 3-D and 4-D may be attributed to H3CIA ligand chelation at the metal center, where red shifts of emission are possibly assigned to different coordination environments around the metal ions.11 As for 2-D, the corresponding emission should be mainly attributed to H3CIA ligand and tmdpy ligand and a slight blue shift was observed. For complexes 1−4 are highly thermally stable and insoluble in common solvents, they may be suitable as excellent candidates for the exploration of blue-fluorescent materials.

Conclusion In this work, two enantiopure organic linkers ((R)-H3CIA and (S)-H3CIA) integrating rigid isophthalate unit and chiral lactate unit have been employed to the construction of four pairs of homochiral MOFs. All the complexes crystallize in three-dimensional metal−organic networks with the help of nitrogen heterocycle auxiliary ligands except complex 1-D and 1-L, which are 2D layered structures containing only tetranuclear Zn2+ centers and CIA3- ligands. The phase and enantiomorphism purities of these complexes are proved by PXRD and CD studies, respectively. Moreover, they exhibit interesting photoluminescent behaviors. The success of our work shows that (R)-H3CIA and (S)-H3CIA can act as a class of effective chiral ligands to construct highly appealed HMOFs.

Acknowledgment. This work was supported by the 973 program (2012CB821705 and 2011CB932504) and NSFC (21221001, 21425102, 21173224, 21473202). Supporting Information Available: IR spectra, TGA, powder X-ray diffraction patterns, and X-ray



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crystallographic files (CCDC 1410236-1410243). This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Author *E-mail: [email protected], [email protected]

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For Table of Contents Use Only

Zhong-Xuan Xu†,‡, Yu Xiao†, Yao Kang†, Lei Zhang†,* and Jian Zhang†,* Two enantiopure organic linkers ((R)-H3CIA and (S)-H3CIA) derived from lactic acid have been synthesized and used to construct four pairs of homochiral metal−organic frameworks (HMOFs) with polymetallic building blocks. Solid-state circular dichroism (CD) and photoluminescent properties are well studied.


Homochiral Cluster-Organic Frameworks Constructed from

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