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Syntheses, Crystal Structures and Physical Properties of Two Noninterpenetrated Pillar-Layered Metal-Organic Frameworks Based on N,N#-Di-(4-Pyridyl)-1,4,5,8-Naphthalenetetracarboxydiimide Pillar Lei Han, Lanping Xu, Lan Qin, Zhao Wen-Na, Xiaozhi Yan, and Lei Yu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg400454c • Publication Date (Web): 06 Aug 2013 Downloaded from http://pubs.acs.org on August 7, 2013

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Crystal Growth & Design

Syntheses, Crystal Structures and Physical Properties of Two Noninterpenetrated Pillar-Layered Metal-Organic Frameworks Based on N,N′-Di-(4-Pyridyl)-1,4,5,8-Naphthalenetetracarboxydiimide Pillar Lei Han,*,† Lan-Ping Xu,† Lan Qin,† Wen-Na Zhao,‡ Xiao-Zhi Yan,† and Lei Yu† †

State Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, P. R. China

‡

Key Laboratory for Molecular Design and Nutrition Engineering of Ningbo, Ningbo Institute of Technology, Zhejiang University, Ningbo, Zhejiang 315100, P. R. China

KEYWORDS: Pillar-layered metal-organic frameworks, eight-connected hex net, six-connected mab net, N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide, 1,4-benzenedicarboxylic acid, 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) ABSTRACT: Two 3D noninterpenetrated pillar-layered metal-organic frameworks have been synthesized

under

solvothermal

reactions

based

on

N,N’-di-(4-pyridyl)-1,4,5,8-

naphthalenetetracarboxydiimide (DPNDI) pillar. Single crystal X-ray diffraction analyses revealed that compound [Co3(BDC)3(DPNDI)(DMF)2]⋅2CH3CN (1) displays an eight-connected hex net with Schläfli symbol 36⋅418⋅53⋅6, and consists of DPNDI pillar and 2D 36 net layer that was constructed from pinwheel trimetallic secondary building unit and 1,4-benzenedicarboxylate (BDC) linker. Compound [Zn2(HFIPBB)2(DPNDI)]⋅8DMF (2) exhibits a six-connected mab net with Schläfli symbol 44⋅610⋅8, and consists of DPNDI pillar and 2D wavelike 44 net layer with helical channels that was constructed from paddlewheel dimetallic secondary building unit and bent V-type 4,4′-(hexafluoroisopropylidene)bis(benzoate) linker. The phase purity, thermal stability and N2 adsorption/desorption of 1 and 2 were measured, the anti-ferromagnetic property of 1 as well as the photochromic phenomenon of 2 have also been investigated and discussed.

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■ INTRODUCTION The assembly of metal-organic frameworks (MOFs) have been a very important issue because of their intriguing structural versatility and their potential applications as functional crystalline materials in gas storage, separation, catalysis, sensor, and drug delivery.1 Crystal engineering using the periodic networks as blueprints in the design and construction of extended porous frameworks has been proved to be very fruitful, especially in the emerging discipline of reticular chemistry.2 It has been demonstrated that one of the most rational methods in construction of porous frameworks is to connect well-defined two-dimensional (2D) layers with appropriate pillars, which is the so-called ‘‘pillaring’’ strategy.3 Various 2D networks, such as 44 grid,4 63 honeycomb,5 kagome net,6 36 net,7 have been widely pillared by rigid dipyridyl ligands, such as 1,4-diazabicyclo-[2.2.2]octane (dabco) and 4,4′-bipyridine (bipy), which results in 3D porous framework structures (Scheme 1). One of the targets in pillaring these 2D networks is to create large voids by using long and rigid organic pillars.4g,8 However, when the single 3D network becomes open, interpenetration usually occurs to achieve close packing.7a,7b Therefore, how to design of 3D pillar-layered MOFs retaining permanent porosity without interpenetration becomes one of the most compelling challenges to chemists. Although several examples on controlling over the interpenetration of porous MOFs have been reported,9 rarely examples were observed on pillar-layered MOFs. To prevent interpenetration, strategies such as using bulky organic building blocks with larger steric hindrances through introducing substituent groups, have been proven successful.10 Alternatively, it is also possible to seek suitable 2D sheets which can avoid interpenetrating by its inherent structural nature. N,N’-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPNDI) is an important bridging ligand in the construction of pillar-layered metal-organic frameworks (Scheme 2).10a,11-13 Several DPNDI-based pillar-layered MOFs have been reported with redox-active properties because DPNDI has an electron-accepting ability, it is possible to form charge-transfer (CT) complexes with electron-donating guest molecules incorporated into the pores.13 Along with our research of the assembly of photochromic metal–organic frameworks based on 1,4,5,8-Naphthalenediimides (NDIs) derivatives,14 our current synthetic strategy is extending to explore the DPNDI ligand that acts as pillar to form 3D pillar-layered MOFs by selecting suitable 2D layers. In this paper, two 3D noninterpenetrated pillar-layered metal-organic frameworks were reported based on DPNDI


2

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pillar and 2D 36 net layer, 2D wavelike 44 net layer, respectively. Compound [Co3(BDC)3(DPNDI)(DMF)2]⋅2CH3CN (1, BDC = 1,4-benzenedicarboxylate) displays an eightconnected

hex

net

and

the

anti-ferromagnetic

property,

compound

[Zn2(HFIPBB)2(DPNDI)]⋅8DMF (2, HFIPBB = 4,4′-(hexafluoroisopropylidene)bis(benzoate)) exhibits a six-connected mab net and the photochromic phenomenon. ■ EXPERIMENTAL SECTION Materials and Physical Measurements. DPNDI was synthesized according to the same procedures reported in the literature.12a Other reagents and solvents employed were commercially available and used as received without further purification. Elemental analyses were carried out on an Elementar Vario EL III analyzer. The IR spectra (KBr pellets) were taken on a Shimadzu FTIR-8900 spectrometer in the range 4000-400 cm-1. Powder X-ray diffraction (PXRD) intensities were measured at room temperature on a Rigaku D/max-IIIA diffratometer (Cu Ka, λ = 1.54056 Å) with a scan rate of 3°/min in the range of 2–54°. Simulated patterns were produced using the Mercury Version 1.4 software (http://www.ccdc.cam.ac.uk/products/mercury/) and single-crystal reflection diffraction data. Thermogravimetric measurements were performed from room temperature to 800℃ on crystalline samples in a nitrogen stream using a Seiko Exstar6000 TG/DTA6300 apparatus at a heating rate of 10℃/min. UV−visible spectra were recorded at room temperature on a PerkinElmer Lambda 900 UV/vis/NIR spectrophotometer equipped with an integrating sphere in the wavelength range of 200−1200 nm. BaSO4 plates were used as a reference (100% reflection), on which the finely ground power of the sample was coated. ESR spectra were recorded on a Bruker ER-420 spectrometer with a 100 kHz magnetic field in X band at room temperature. The variable-temperature magnetic-susceptibility data were measured with a Quantum Design MPMS7 SQUID magnetometer. Magnetic measurements were performed on samples of crushed single crystals in the 2-300 K range. The photoluminescent properties were measured on a Perkin-Elmer LS55 spectrometer. Synthesis of [Co3(BDC)3(DPNDI)(DMF)2]⋅⋅2CH3CN (1). A mixture of Co(NO3)2·6H2O (43.8 mg, 0.15 mmol), DPNDI (21.3 mg, 0.05 mmol), and H2BDC (9.1 mg, 0.055 mmol) in DMF/CH3CN (8 ml; 3:1) solution was stirred for an hour. The mixture was sealed in a 25 ml Teflon -lined steel-steel reactor and heated at 80℃ for 5 days. The crude product was washed


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with DMF to give red block-like crystals of 1. The yield is ca. 77 % based on DPNDI. Anal. Calcd. for Co3C58H44N8O18(%): C 52.86, H 3.37, N 8.50; found (%): C 52.71, H 3.48, N 8.32. IR(KBr, cm-1): 3430(m), 1720(s), 1680(vs), 1568(vs), 1384(s), 1242(s), 840(m), 746(m), 622(w), 522(w). Synthesis of [Zn2(HFIPBB)2(DPNDI)]⋅⋅8DMF (2). A mixture of Zn(NO3)2·6H2O(29.4 mg, 0.1 mmol), H2HFIPBB (39.1mg, 0.1 mmol) and DPNDI (20.6 mg, 0.05 mmol) in DMF (6 mL) was sealed in a Teflon-lined stainless-steel reactor and heated at 80℃ for 5 days. After the solution was cooled to room temperature, pale-yellow single crystals of 2 were obtained. The yield is ca. 60 % based on DPNDI. Anal. Calcd. for Zn2C58H28F12N4O12⋅C24H56N8O8 (%): C 51.39, H 4.42, N 8.77; found (%): C 51.24, H 4.51, N 8.99. IR(KBr, cm-1): 3417(m), 1720(s), 1679(vs), 1609(vs), 1343(s), 1247(vs), 1168(s), 960(w), 784(m), 723(w). Single-Crystal X-ray Diffraction. The diffraction data of 1 and 2 were collected on a Bruker Apex II CCD area-detector diffractometer (Mo Kα, λ = 0.71073 Å).15 Absorption correction was applied by using multi-scan program SADABS.16 The structure was solved with direct methods and refined with a full-matrix least-squares technique with the SHELXTL program package.17 Anisotropic thermal parameters were applied to all non-hydrogen atoms of 1 and 2. The positions of H atoms were generated geometrically, assigned isotropic thermal parameters, and allowed to ride on their parent carbon atoms before the final cycle of refinement. The naphthalene ring, DMF and CH3CN molecules in compound 1 are disordered. Even though the electron densities of some guest solvent molecules were found, those could not be well modeled in the refinement because of severe disorder. The final refinement was performed with modification of the structure factors for contribution of the disordered solvent electron densities using the SQUEEZE option of PLATON.18 The crystal data of 1 and 2 are summarized in Table 1. Further crystallographic details for the structure reported in this paper can be obtained from the Cambridge Crystallographic

Data

Center

(www.ccdc.cam.ac.uk/conts/retrieving.html,

E-mail:

[email protected]), on quoting the depository numbers CCDC 929355 for 1 and 929356 for 2. ■ RESULTS AND DISCUSSION


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Synthetic Strategy. To construct pillar-layered MOFs using DPNDI, the selection of suitable 2D layers is very critical. Through the research of literatures, we found that the classical 44 grid layer constructed with 1,4-benzenedicarboxylic acid (BDC) (Scheme 2) and paddlewheel SBU can be pillared by DPNDI ligand to form a 3D pillar-layered framework, which displays interpenetrated structure due to the large window of 44 grid and the long DPNDI pillar.10c If the size of window in 2D layer were decreased to small size, the noninterpenetrated 3D framework could be designed and constructed with DPNDI pillar. To verify our hypothesis, we chose the 2D 36 net formed with pinwheel trimetallic cluster SBU and BDC ligand as layer in view of its smaller trigonal windows. In the 2D 36 layer reported,7,19 the terminal solvent sites on both ends of the trimetallic centers may be replaced by linear bipyridyl molecules, and we expect that this type of neutral 2D layers would be ideal candidates to construct pillar-layered frameworks. With this in mind, we treated the solvothermal reaction with Co(NO3)2·6H2O, H2BDC and DPNDI in mixed DMF/CH3CN solvents, the anticipated complex 1 was collected. On the other hand, our previously reported works20 have been focused on the 4,4′(hexafluoroisopropylidene)bis(benzoate) ligand. The bent V-type HFIPBB ligand is an excellent candidate for the construction of 2D wavelike 44 net layers with helical channels supported by the paddlewheel dimetallic SBU.20a,21 Furthermore, these 2D networks can be transferred into 3D MOFs if pillared by N-donor linear ligands.22,23 However, the 2D wavelike 44 net layers usually display interpenetrated or self-penetrating structures in these 3D MOFs, especially in 3D MOFs pillared with N-donor ligands,20a,

23

because of the long and bent feature of HFIPBB ligand.

Considering that the large naphthalenetetracarboxydiimide group in DPNDI ligand, we expect that the noninterpenetrated pillar-layered MOFs would be constructed and controlled with larger steric hindrances. With this in mind, we treated the solvothermal reaction with Zn(NO3)2·6H2O, H2HFIPBB and DPNDI in DMF, and successfully obtained the complex 2. Crystal Structures of 1. Single-crystal X-ray diffraction analyses revealed that 1 consists of 2D triangle-tessellated networks based on pinwheel [Co3(CO2)6O2N2] SBUs. Figure 1 illustrates the coordination environment of the Co atoms and the geometry of the trinuclear SBU unit. The SBU contains a linear array of three Co atoms lying on a 2-fold axis. The central Co2 atom resides at a crystallographic inversion centre and assumes an octahedral coordination environment with six symmetry-equivalent carboxylate oxygens from six different BDC ligands. Each of the two


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symmetry-related terminal Co atoms (Co1 and Co1A) is bound to four carboxylate oxygens, one oxygen atom from DMF and one pyridine nitrogen atom to form a distorted octahedral geometry. The Co–O bond distances range from 2.022(5) to 2.187(5) Å, while the Co–N distance is 2.079(6) Å. The three Co atoms are bridged by six carboxylates to form a trinuclear [Co3(CO2)6O2N2] SBU with the pinwheel structure, in which the carboxylate bridges adopt two kinds of coordination modes and the adjacent Co⋅⋅⋅Co distance is 3.520(5) Å. Each trinuclear SBU is connected to six BDC units to form a triangle-tessellated layer structure with smaller trigonal windows (Figure 2a). Taking the trinuclear motifs as 6-connecting nodes and the ligands as linkers, the layer can be considered to be a 36 net. Therefore, this layer is pillared by DPNDI to result in a 3D noninterpenetrated framework in spite of the long feature of DPNDI linker (Figure 2b). In the resulting pillar-layered framework, the trinuclear SBUs act as 8-connected nodes to generate the 3D hex topology with Schläfli symbol 36⋅418⋅53⋅6, as shown Figure 2c. To the best of our knowledge, the pillared 2D 36 layer in metal−organic frameworks is rarely observed,7 and the complex 1 is the first example of DPNDI-based MOFs with 2D 36 net. The total solventaccessible volume in this noninterpenetrated framework accounts approximately 39.1 % of the whole crystal volume as estimated by PLATON.24 The N2 sorption at 77 K for 1 was activated by evacuating a freshly prepared sample at 200 °C under a dynamic vacuum overnight. Fittings of the Brunauer−Emmett−Teller equation to the adsorption isotherms of N2 (Figure 5a) give an estimated surface area of 755.6 m2/g, which confirms the existence of micropores in 1. The guest CH3CN molecules are located in pores of framework. According to elemental analysis (EA) and thermogravimetric analysis (TGA), the solvent molecules were proposed to be two CH3CN molecules. Crystal Structures of 2. Single-crystal X-ray diffraction analyses revealed that 2 consists of 2D 44 networks based on paddlewheel [Zn2(CO2)4N2] SBUs. As displayed in Figure 3, the coordination geometry of each Zn atom in the paddlewheel is in square pyramid, the square plane of which comprises four oxygen atoms from carboxylate groups of four HFIPBB ligands, and the apical coordination site is filled by one nitrogen atom from the DPNDI ligand with a Zn−N distance of 2.038(4) Å. The Zn−O bond lengths in the SBUs vary in the range of 2.012(4) −2.056(4) Å, and the intradimer Zn−Zn separation is 2.9845(10) Å. The dihedral angle between the bent rings of the HFIPBB ligand is 66.2°; these bent HFIPBB moieties link four other neighboring paddlewheels resulting in a 2D 44 net with dimensions 10.64 Å × 10.65 Å (Figure


6

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4a). The skeleton of the 2D layer can also be viewed that it is constructed from helical tubes with 1D channels. These noninterpenetrated 2D layers are extended to a 3D framework pillared by DPNDI ligand (Figure 4b). The two pyridine rings in the DPNDI ligand twist from the naphthalenetetracarboxydiimide plane, and the dihedral angles between the planes of the pyridine rings and the plane of naphthalenetetracarboxydiimide group are 116.7°. Paddlewheel SBUs are considered as six-connected nodes and the 3D framework of 2 exhibits a mab topology with Schläfli symbol 44⋅610⋅8, as shown Figure 4c. It is worth noting that the present mab net is closely related to the nets roa, net B and net C (personal appointment). All above-mentioned nets have the

same

Schläfli

symbol

44⋅610⋅8,

but

with

different

long

vertex

symbols

(4.4.4.4.64.64.65.65.65.65.611.611.611.611 for mab,25 4.4.4.4.62.62.65.65.65.65.65.65.65.65 for roa,26 4.4.4.4.63.63.65.65.65.65.66.66.66.66.89 for net B,27 and 4.4.4.4.64.64.65.65.65.65.65.65.65.65.820 for net C28). The total solvent-accessible volume in the framework of 2 accounts approximately 63.3 % of the whole crystal volume as estimated by PLATON.24 According to elemental analysis (EA) and thermogravimetric analysis (TGA), the solvent molecules were proposed to be eight DMF molecules. The N2 sorption at 77 K for 2 was activated by evacuating a freshly prepared sample at 200 °C under a dynamic vacuum overnight. Fittings of the Brunauer−Emmett−Teller equation to the adsorption isotherms of N2 (Figure 5b) give an estimated surface area of 335.7 m2/g. To the best of our knowledge, the structure of 2 is the first example of pillar-layered MOF containing noninterpenetrated 2D wavelike 44 net based on HFIPBB linker.23 Physical properties of 1. Powder X–ray diffraction (PXRD) experiments on the bulk material of 1 showed that all major peaks match well with simulated PXRD, indicating its crystalline phase purity (Figure 6a). TGA of the as-synthesized sample showed a sharp weight loss of 21.84% between 20 and 290 °C, corresponding to the removal of two lattice CH3CN and two coordinated DMF molecules (calcd 22.18%). A sharp weight loss occurred starting from 300 °C indicating the collapse of whole frameworks (Figure 6b). The preliminary magnetic properties of complex 1 are shown in Figure 6c and 6d. The temperature dependence of magnetic susceptibility from 2.0 to 300 K was measured on a SQUID magnetometer at a field of H = 1 kOe. The χMT value at room temperature is 4.94 cm3 mol-1 K. On cooling, the χMT value decreases continuously from 300 K down to 2.0 K, reaching 0.11 cm3 mol-1 K at 2.0 K, indicating the presence of an antiferromagnetic coupling. The value of χM above 100 K obeys the Curie-Weiss Law, χM = C / (T − θ), with a Curie constant C = 8.46 cm3 mol-1 K and a Weiss constant θ = -211.04 K. The


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negative Weiss constant indicates that the anti-ferromagnetic coupling dominates the major exchanges between Co2+ centers. The room temperature effective moment (µ eff) is 6.28 µ B. Furthermore, the anti-ferromagnetic nature of 1 is further supported by M vs H plot at 2 K (Figure 6d). The magnetization is 0.52 Nβ at H = 70 kOe, which is far smaller than the saturated value of three cobalt ions under moderate external fields. No detectable hysteresis and no long range ordering was observed, which is consistent with the overall anti-ferromagnetic interactions between Co(II) ions. Physical properties of 2. PXRD experiments on the bulk material of 2 showed that the structure of 2 in powder has a little change than in crystalline state, its XRD peaks becomes broad (Figure 7a). The reason may be that the guest solvents were lost when the single crystals of 2 were grounded onto powder. TGA of the as-synthesized sample 2 shows that a sharp weight loss of 29.49% before 355 °C, corresponding to the removal of four lattice DMF molecules (calcd 29.78%), then the whole framework of 2 begins to collapse (Figure 7b). Interestingly, 2 is sensitive to sunlight and undergoes a photochromic transformation from yellow to dark green (2′) upon irradiation by sunlight for a few minutes (Figure 7c). The sample 2′ can return to yellow in a

dark

room

for

several

days

at

ambient

temperature.

As

known,

1,4,5,8-

naphthalenetetracarboxydiimide (NDI) is redox-active and can generate radicals upon light irradiation.29 Therefore, the photochormic process may arise from the photo–induced radical generation of organic ligands. This radical generation has been confirmed by ESR spectra (Figure 7d). Complex 2 exhibits no ESR signal, but 2′ shows a single–peak radical signal with a g value of 2.0056. UV/Vis spectrum of 2 shows strong absorption bands at 260 and 330 nm, corresponding to the n–π* and π–π* transition of the aromatic organic ligands (Figure 7e). The UV/Vis spectrum of 2′ displays a broad absorption band at 600 nm, which may arises from the photo-induced electron–transfer transition.14 The fluorescent properties of HFIPBB, DPNDI and 2 have also been investigated in the solid state at room temperature. As shown in Figure 7f, 2 exhibits emission peak at 415 nm (λex = 360 nm), which shows the large red shift compared with the HFIPBB ligand emission (λem = 320 nm, λex = 290 nm), and the blue shift compared with the DPNDI ligand emission (λem = 430 nm, λex = 370 nm). These emissions could be assigned to the ligand-to-metal charge transfer (LMCT).30 ■ CONCLUSION


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In conclusion, two interesting noninterpenetrated metal-organic framework were designed and assembled by using DPNDI pillar. Two pillar-layered frameworks display eight-connected hex net and six-connected mab net, respectively. Compound 1 displays the anti-ferromagnetic property and 2 exhibits the photochromic phenomenon. The strategy on controlling over interpenetration via rational design of the 2D sheets is introduced in this article, and the construction of 3D pillar-layered MOFs from DPNDI and other type 2D sheets are underway. ASSOCIATED CONTENT Supporting Information. Crystal structure data CIF file for 1. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]. Tel: +86-574-87600782. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (No. 21071087, 91122012), the Scientific Research Foundation for the Returned Overseas Chinese Scholars, the Outstanding Dissertation Growth Fundation of Ningbo University (No. PY2012017), and the K.C. Wong MagnaFund in Ningbo University. REFERENCES (1) (a) O′Keeffe, M.; Yaghi, O. M. Chem. Rev. 2012, 112, 675−702. (b) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R. Chem. Rev. 2012, 112, 724−781. (c) Li, J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012, 112, 869−932. (d) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105−1125. (e) Yoon, M.; Srirambalaji, R.; Kim, K. Chem. Rev. 2012, 112, 1196−1231. (f) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Férey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232−1268. (g) Almeida Paz, F. A.; Klinowski, J.; Vilela, S. M. F.; Tomé, J. P. C.; Cavaleiro, J. A. S.; Rocha, J. Chem. Soc. Rev. 2012, 41, 1088–1110.


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Scheme 1. Representation of pillar-layered MOF and 2D sheet nets.

Scheme 2. The molecular structures of DPNDI, BDC and HFIPBB.


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Table 1. Crystallographic data for 1 and 2. 1

2*

Empirical formula

Co3C58H44N8O18

Zn2C58H28F12N4O12

Formula weight

1317.80

1331.58

Temperature (K)

298(2)

298(2)

Wavelength (Å)

0.71073

0.71073

Crystal system

monoclinic

orthorhombic

Space group

C2/c

Pbcn

a (Å)

47.400(4)

16.4070(8)

b (Å)

9.6110(7)

22.5138(15)

c (Å)

17.8051(13)

30.5117(19)

α (°)

90

90

β (°)

92.2100(10)

90

90

90

V (Å )

8105.3(10)

11270.5(12)

Z

4

4

Dcalc (g⋅cm-3)

1.080

0.785

F(000)

2692

2672

µ (mm )

0.665

0.479

θ Range (°)

2.41―25.02

2.94―25.02

h

-56 ≤ h ≤ 52

-19 ≤ h ≤ 10

k

-11 ≤ k ≤ 6

-26 ≤ k ≤ 17

l

-21 ≤ l ≤ 21

-28 ≤ l ≤ 36

Reflections collected

20671

24664

Unique reflections

7148 [Rint = 0.1588]

9942 [Rint = 0.0724]

Data / restraints / parameters

7148 / 0 / 510

9942 / 0 / 397

S

1.035

0.971

R1, wR2 [I ≥ 2σ(I)]

0.0752, 0.1631

0.0947, 0.2635

R1, wR2 (all data)

0.1592, 0.1755

0.1465, 0.3007

Largest peak, hole (e.Å-3)

0.705, -0.515

1.103, -0.458

γ (°) 3

–1

*As the highly disordered solvent molecules in 2 could not be modeled, the PLATON/SQUEEZE procedure was used to remove the contribution of reflection by DMF molecules. The chemical formula of 2 was estimated from the result of the SQUEEZE procedure combined with the results of EA and TGA.


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Figure 1. View of the structure of trinuclear pinwheel SBU and the coordination environment of Co centers in 1. Hydrogen atoms were omitted for clarity. Symmetry code: A -x+3/2, -y+3/2, z+1.

Figure 2. (a) 2D 36 net in 1. (c) 3D pillar-layered framework of 1. (d) Representation of 8connected hex net with Schläfli symbol 36⋅418⋅53⋅6.


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Figure 3. View of the structure of dinuclear paddlewheel SBU in 2 and the coordination environment of Zn centers. Hydrogen atoms were omitted for clarity. Symmetry code: A -x, y, z+1/2; B x-1/2, y-1/2, -z+1/2; C -x+1/2, y-1/2, z.

Figure 4. (a) 2D 44 net with helical chains in 2. (b) 3D pillar-layered framework of 2 with 1D channels. (d) Representation of 6-connected mab net with Schläfli symbol 44⋅610⋅8.


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Figure 5. Adsorption/desorption isotherm of N2 for activated 1 (a) and 2 (b) at 77 K.


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Figure 6. (a) PXRD patterns. (b) TG curve of 1. (c) Temperature dependency of χMT and χM-1 for 1 at H = 1 kOe from 2.0―300 K. The red solid line represents the best fit to the Curie-Weiss Law mentioned in the text. (d) Field-dependency of magnetization of 1 at 2.0 K.


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Figure 7. (a) PXRD patterns. (b) TG curve of 2. (c) Photographic images show the photochromic effect of single crystals of 2. (d) ESR spectra for 2 and 2′. (e) UV/Vis spectra of 2 and 2′. (f) Emission spectra of HFIPBB, DPNDI and compound 2.


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SYNOPSIS Two noninterpenetrated pillar-layered metal-organic frameworks were designed and assembled by using N,N’-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPNDI) as pillar. Compound 1 displays eight-connected hex net and the anti-ferromagnetic property, while 2 exhibits six-connected mab net and the photochromic phenomenon.


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Syntheses, Crystal Structures, and Physical ... - ACS Publications

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