A Unique Optical and Electrical Multifunctional Metal−Organic

Apr 9, 2010 - Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. China. Received ... that exhibit excellent electrical and ...
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DOI: 10.1021/cg901605j

A Unique Optical and Electrical Multifunctional Metal-Organic Framework Based on Polynuclear Rod-Shaped Secondary Building Units Constructed from a “Three Birds with One Stone” in Situ Reaction Process

2010, Vol. 10 2272–2277

Xinxin Xu,† Xia Zhang,† Xiaoxia Liu,*,† Ting Sun,† and Enbo Wang‡ †

Department of Chemistry, College of Science, Northeast University, Shenyang, Liaoning, 110004, People’s Republic of China, and ‡Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. China Received December 20, 2009; Revised Manuscript Received March 19, 2010

ABSTRACT: A unique three-dimensional metal-organic framework (MOF) [Cd4(1,100 -phen)(fum)(S-mal)(R-mal)(H2O)] (1) (1,100 -phen =1,10-phenanthroline, fum = fumarate dianion, mal = malate dianion) has been synthesized and characterized by single-crystal X-ray analysis. Under hydrothermal conditions, after a “three birds with one stone” in situ reaction process, maleic acid turns into fumarate dianion, isomeric R-malate dianion and S-malate dianion, which further connect with Cd atoms and form an octanuclear Cd cluster. The octanuclear Cd cluster links with neighboring clusters and constructs a rod-shaped secondary building unit (SBU). Neighboring rod-shaped SBUs are further connected by fumarate dianions and thus forms a three-dimensional network. To our interests, complex 1 exhibits interesting semiconductivity and fluorescence properties. When citraconic acid was used instead of maleic acid, a new complex [Cd2(mesac)2(1,100 -phen)2] (2) (mesac = mesaconate dianion) was synthesized under about the same reaction conditions. Complex 2 also exhibits fluorescence properties.

Introduction Immense interest in metal-organic frameworks (MOFs) originate not only from their intriguing variety of molecular architectures and topologies but also because of their potential applications as functional materials.1,2 Inspired by this, in the past decades, a lot of MOFs with various functions, such as hydrogen storage, selective molecular separation, ion exchange, catalysis, magnetism, and fluorescence have been synthesized.3-6 Nowadays, researchers want to combine as many as possible properties into one MOF, namely, multifunctional MOF, for their burgeoning applications in much more areas compared with MOFs that possess only a single property.7 Our interest is the pursuit of multifunctional MOFs that exhibit excellent electrical and optical properties. To our knowledge, the interactions between metal ions in extended solid structures may lead to special magnetism, fluorescence, and electrical conductivity behavior.8 So we can conclude that MOFs constructed from rod-shaped secondary building units (SBUs), especially high nuclear rod-shaped SBUs, which have multiple metal-metal interactions, may exhibit outstanding electrical and optical properties.9 Although some MOFs based on rod-shaped SBUs have been reported, studies on such kinds of MOFs are still in their infancy and MOFs constructed from high nuclear rod-shaped SBUs have seldom been reported.10,11 Fortunately, with an interesting “three birds with one stone” in situ reaction process, we have synthesized such a complex, namely, [Cd4(1,100 -phen)(fum)(S-mal)(R-mal)(H2O)] (1) (1,100 -phen = 1,10-phenanthroline, fum = fumarate dianion, mal = malate dianion). To our interest, this complex consists of rod-shaped SBUs which are constructed by an octanuclear Cd cluster and exhibits interesting semiconductivity and fluorescence properties. When citraconic acid was used instead of maleic acid, *Author to whom correspondence should be addressed. Tel: þ86-02483689510. Fax: þ86-024-23600159. E-mail: [email protected]. pubs.acs.org/crystal

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under about the same condition, another new complex [Cd2(mesac)2(1,100 -phen)2] (2) (mesac = mesaconate dianion) was also synthesized, which shows fluorescence properties. Experimental Section Materials and Methods. All purchased chemicals were of reagent grade and used without further purification. Elemental analyses (C, H, and N) were performed on a Perkin-Elmer 2400 CHN elemental analyzer. FT/IR spectra were recorded in the range 4000-400 cm-1 on an Alpha Centaur FTIR spectrophotometer using KBr pellets. Thermogravimetric analyses were performed on a Perkin-Elmer TGA7 instrument in flowing N2 with a heating rate of 10 °C min-1. Powder X-ray diffraction (PXRD) patterns were recorded on a Siemens D5005 diffractometer with Cu KR (λ = 1.5418 A˚) radiation in the range of 3-50°. Photoluminescence spectra were measured using a FL-2T2 instrument (SPEX, USA) with 450-W xenon lamp monochromatized by double grating (1200 gr/mu). The conductivity measurements were performed by conventional fourprobe techniques. Synthesis of [Cd4(1,100 -phen)(fum)(S-mal)(R-mal)(H2O)] (1). Complex 1 was prepared from a mixture of Cd(OAc)2 3 2H2O (0.11 g, 0.40 mmol), maleic acid (0.093 g, 0.80 mmol), 1,100 -phen (0.144 g, 0.80 mmol), and 8 mL of H2O. The mixture was stirred and the pH value was adjusted to 7 with 2 M NaOH. After being stirred for another 20 min, the mixture was transferred to a 23 mL Teflonlined stainless steel bomb and kept at 160 °C under autogenously pressure for 6 days. The reaction system was cooled to room temperature during 24 h. A large amount of yellow crystals of 1 were obtained. Yield: 0.069 g, 67% (based on Cd). Anal. Calcd for C24H18Cd4N2O15: C, 28.15%; H, 1.77%; N, 2.74%. Found: C, 28.24%; H, 1.81%; N, 2.81%. The purity of complex 1 was confirmed by similarities between its simulated and experimental PXRD (Figure S5, Supporting Information). Synthesis of [Cd2(mesac)2(1,100 -phen)2]n (2). Colorless crystals of 2 suitable for X-ray analysis were obtained by a method similar to the one described for 1, except that citraconic acid was used instead of maleic acid to react with Cd(OAc)2 3 2H2O and 1,100 -phen. Yield: 0.106 g, 63% (based on Cd). Anal. Calcd for C34H24Cd2N4O8: C, 48.57%; H, 2.88%; N, 6.66%. Found: C, 48.61%; H, 2.92%; N, 6.61%. The purity of complex 2 was confirmed by similarities r 2010 American Chemical Society

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Table 1. Crystal Data and Structure Refinement for 1 and 2a param empirical formula formula weight crystal system space group a/A˚ b/A˚ c/A˚ R/° β/° γ/° V/A˚3 Z Dcalcd/(g cm-3) F (000) reflections collected reflections unique R (int) completeness data/restraints/parameters goodness-of-fit on F2 R1 [I > 2σ(I)] wR2 [I > 2σ(I)] R1 (all data) wR2 (all data)

2 C34H24N4O8Cd2 841.37 orthorhombic Pca21 15.541(3) 10.139(2) 19.705(4) 90 90 90 3105.0(11) 4 1.800 1664 22772 5392 0.0570 99.0% 5392/131/405 1.049 0.0461 0.1441 0.0481 0.1460

Table 2. Selected Bond Lengths for 1 and 2a 1 Cd(1)-O(2) Cd(1)-O(5) Cd(1)-O(10) Cd(2)-O(4) Cd(2)-O(8) Cd(2)-O(12) Cd(3)-O(3)#1 Cd(3)-O(8) Cd(3)-O(9)#1 Cd(4)-O(1) Cd(4)-O(6) Cd(4)-O(15) Cd(4)-N(2)

2.278(5) 2.285(4) 2.182(5) 2.337(5) 2.287(5) 2.179(6) 2.250(5) 2.357(5) 2.327(4) 2.476(6) 2.371(4) 2.311(6) 2.311(6)

Cd(1)-O(3) Cd(1)-O(6) Cd(1)-O(8) Cd(1)-N(4) Cd(2)-O(2) Cd(2)-O(4) Cd(2)-N(1)

2.373(6) 2.362(5) 2.221(4) 2.373(6) 2.272(4) 2.503(5) 2.360(7)

Cd(1)-O(4) Cd(1)-O(5)#2 Cd(1)-O(11)#2 Cd(2)-O(5)#2 Cd(2)-O(9)#1 Cd(2)-O(14) Cd(3)-O(6)#1 Cd(3)-O(9) Cd(3)-O(13) Cd(4)-O(2) Cd(4)-O(7) Cd(4)-N(1)

2.422(5) 2.287(5) 2.198(6) 2.214(5) 2.258(4) 2.231(6) 2.303(5) 2.284(4) 2.248(5) 2.486(5) 2.401(6) 2.357(6)

Cd(1)-O(5) Cd(1)-O(7) Cd(1)-N(3) Cd(2)-O(1) Cd(2)-O(3) Cd(2)-O(6) Cd(2)-N(2)

2.433(5) 2.562(6) 2.336(6) 2.481(6) 2.333(5) 2.421(6) 2.338(5)

2

a Symmetry transformations used to generate equivalent atoms for complex 1: #1: -x, -y, -z þ 2; #2: -x - 1, -y, -z þ 2.

)

R1 = Σ Fo| - |Fc /Σ|Fo|; wR2 = Σ[w(Fo2 - Fc2)2]/Σ[w(Fo2)2]1/2. )

a

1 C24H18Cd4N2O15 1024.00 triclinic P1 10.820(2) 11.416(2) 12.432(3) 87.44(3) 72.45(3) 70.11(3) 1374.0(5) 2 2.475 976 10718 4807 0.0291 99.1% 4807/3/412 1.106 0.0397 0.1564 0.0446 0.1654

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between its simulated and experimental PXRD (Figure S6, Supporting Information). X-ray Crystallography. Suitable single crystals of 1 and 2 were carefully selected under an optical microscope and glued on glass fibers. Structural measurements were performed on a Bruker AXS SMART APEX II CCD diffractometer at 293 K. The structures were solved by the direct method and refined by the full-matrix least-squares method on F2 using the SHELXTL 97 crystallographic software package.12 Anisotropic thermal parameters were used to refine all non-hydrogen atoms. Carbon-bound hydrogen atoms were placed in geometrically calculated positions; oxygenbound hydrogen atoms were located in the difference Fourier maps, kept in that position, and refined with isotropic temperature factors. Further details of X-ray structural analysis are given in Table 1. Selected bond lengths are listed in Table 2. Further details of the crystal structure determination have been deposited with the Cambridge Crystallographic Data Centre as a supplementary publication. CCDC 746617 and 721340 for complexes 1 and 2 contain the supplementary crystallographic data for this paper.

Results and Discussion Single crystal X-ray analysis shows that four distinct unique Cd atoms exist in the fundamental unit (Figure 1a). Cd(1) connects with three carboxylate oxygen atoms and two hydroxyl oxygen atoms from malate dianions, one carboxylate oxygen atom from fumarate dianion. This results in a distorted octahedronal coordination mode of Cd(1). Cd(2) and Cd(3) adopt the same kind of coordination mode with Cd(1), but with different bond lengths and angles. Cd(4) exists in distorted pentagonal bipyramidal geometry, being ligated by four carboxylate oxygen atoms from different malate dianions, two pyridyl nitrogen atoms from 1,100 -phen and one water molecule. Moreover, in malate dianion, carboxylate groups with two kinds of coordination modes have been found; one is bridging and the other chelating-bridging. At the same time, the hydroxyl group also coordinates with Cd atoms. With this kind of connection mode, four Cd atoms and their symmetry-related atoms (Cd1A, Cd2A, Cd3A, and Cd4A generated by the symmetry operation -1 - x, -y, 2 - z) are connected and form an interesting octanuclear Cd cluster (Figure 1b). The [Cd8(R-mal)2(S-mal)2(CO2)2] cluster has a size about 11.1  10.0  6.2 A˚ between corner metal

Figure 1. (a) Ball-and-stick representation of the coordination environments of Cd(1), Cd(2), Cd(3), and Cd(4) in complex 1; (b) polyhedron representation of the octanuclear Cd cluster of complex 1. Hydrogen atoms are omitted for clarity.

sites, which is the second largest cadmium-carboxylate cluster made so far after the undecanuclear [Cd11(μ4-HCOO-)6(CO2)18] cluster. As such, each octanuclear Cd cluster links

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Figure 2. Infinite rod-shaped secondary building blocks used to assemble complex 1: (a) SBU shown as polyhedron; (b) ball-andstick representation of SBU highlighted the Cd 3 3 3 Cd interactions.

with two neighboring clusters and constructs a rod-shaped secondary building unit (SBU) (Figure 2a). In this rod-shaped SBU, the adjacent Cd atoms are connected with Cd 3 3 3 Cd interactions, with Cd1-Cd2 3.462 A˚, Cd2-Cd3 3.399 A˚, Cd3-Cd3a 3.378 A˚, and Cd1-Cd1a 3.302 A˚ (Figure 2b). Each rod-shaped SBU is further linked to neighboring rodshaped SBUs with fumarate dianions and thus forms a threedimensional network. The structure of complex 1 has channels of 12.5  11.4 A˚ dimensions with a void space running along the a axis and the channels are occupied by 1,100 -phen ligands, which coordinate to Cd(4) atoms (Figure 3a,b). Up to now, some reports on MOFs constructed from rodshaped SBUs have been reported, but none of them possesses high nuclear rod-shaped SBUs. Consequently, this represents the first and only example of MOF constructed from high nuclear rod-shaped SBUs, and this net also represents the biggest rod-shaped SBU based MOF of any known species. Another striking character of complex 1 is the simultaneous “capture” of fumarate dianion, isomeric R-malate dianion and S-malate dianion that originate from the in situ reaction of maleic acid under hydrothermal conditions (Scheme 1). Although in situ reaction synthesis has received great interest in the past decade and some reactions of maleic acid, such as conformation transform and adding with water molecular have been documented, such “three birds with one stone” in situ reaction process has rarely been reported in the literature.13 After comparing the structure of complex 1 with other coordination polymers built from rod-shaped SBUs, we found that the effects of organic molecules is an important factor in determining the special topology of complex 1: First, the CHdCH double bond is an active group, which can add with water molecule and form malic acid under hydrothermal conditions.14 The malic acid possesses not only a strong coordination ability, but also special connection modes, which can link more metal ions together and form a high nuclear rod-shaped SBU. Second, the conformation of maleic acid can transform from cis to trans and produce rigid fumaric aicd, which will further link various SBUs to a 3D MOF.15 Further study indicates the influence of the pH value on the structure of complex 1 is also obvious. Under neutral conditions, complex 1 was obtained; however, under basic conditions, an interesting 2D complex [Cd(fum)(phen)]n was

Figure 3. The 3D framework of complex 1 and hydrogen atoms are omitted for clarity: (a) along the a axis; (b) along the c axis.

Scheme 1. With a “Three Birds with One Stone” in Situ Position Reaction of Complex 1, Maleic Acid Turns into Fumarate Dianion, Isomeric R-Malate Dianion and S-Malate Dianion

synthesized.14d This can be attributed to the different reaction activities of maleic acid under various acidities. Under the appropriate pH value, maleic acid not only can exhibit conformation transformation, but also can combine with a water molecule and form malic acid. However, under high pH values, the second reaction cannot happen. When citraconic acid was used instead of maleic acid, complex 2 was synthesized under about the same reaction conditions. In this complex, the mesaconate dianion coordinates to Cd atoms directly. As no mesaconic acid was added to the starting reaction mixture, we can conclude the mesaconate dianion generates from the conformation transform reaction

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Figure 5. (a) The fluorescence property of complex 1; (b) the fluorescence property of complex 2.

Figure 4. (a) The coordination environment of Cd(1) and Cd(2) in complex 2 and all the hydrogen atoms are omitted for clarity; (b) the 1D twisted double chain; (c) the 2D supramolecular layer structure formed by a 1D twisted double chain.

of citraconic acid. The structure of complex 2 is an interesting twisted double chain, and this complex crystallizes in the Pca21 space group. Its fundamental unit is made up of two crystallographically independent Cd atoms, two mesaconate dianions, and two 1,100 -phen ligands. As shown in Figure 4a, each Cd(1) atom adopts a distorted pentagonal-bipyramidal coordination sphere consisting of five carboxylate oxygen atoms from three different mesaconate dianions. The Cd-O bond distances range from 2.226 to 2.542 A˚. Two nitrogen atoms from 1,100 -phen ligand occupy the other two coordination sites with an average Cd-N bond distance of 2.356 A˚. Cd(2) adopts the same kind of coordination mode with Cd(1) but with different bond lengths and angles. Cd(1) and Cd(2) are bridged by two carboxylate groups separately from two crystallographically equivalent mesaconate dianions and generate a double Cd cluster. Two carboxylate groups of mesaconate dianion both adopt chelating-bridging coordination modes. With this kind of connection mode, mesaconate dianion link the adjacent double Cd clusters together and form a one-dimensional double chain-like structure as shown in Figure 4b. There are π-π stacking interactions in the structure of the twisted double chain (intrachain π-π stacking interactions). The plane-plane distance between two adjacent 1,100 -phen ligands in a twisted double chain is 3.655 A˚, which is reasonable and may be crucially important in the formation of the double Cd cluster of complex 2. And π-π stacking

interactions also exist between neighboring twisted double chains. The plane-plane distance between two 1,100 -phen ligands separately from two neighboring twisted double chains is 3.612 A˚. With the π-π interactions, one-dimensional chains connect together and result in a two-dimensional supramolecular layer as shown in Figure 4c. The IR spectrum of 1 exhibits strong bands at 1548, 1504 and 1442, 1407 cm-1, which can be attributed to the antisymmetric and symmetric stretching vibrations respectively (Figure S1, Supporting Information). The separations (Δ) between γasym (CO2) and γsym (CO2) are 62 and 141 cm-1, respectively. These values are in agreement with the coordination modes of the organic ligands. Unlike complex 1, the IR spectrum of complex 2 shows strong bands at 1579 and 1528, 1425 cm-1. This can be attributed to the antisymmetric and symmetric stretching vibrations respectively (Figure S2, Supporting Information). The Δ values are 51 and 154 cm-1, which are also in agreement with the coordination modes of the organic ligands. In order to examine the stability of the framework, thermal gravimetric analysis (TGA) was carried out in nitrogen gas from 30 to 700 °C (Figure S3, S4, Supporting Information). For complex 1, the TG curve shows that the first weight loss 1.67% in the temperature range of 148-166 °C is due to the loss of water molecules (calcd 1.76%). The PXRD pattern reveals that even after the loss of water molecules, the whole MOF does not collapse (Figure S5c, Supporting Information). Over the range of 323-395 °C, the weight loss 54.21% should correspond to the decomposition of organic ligands (calcd 54.30%). Complex 2 displays a one-step weight loss about 73.19% from 328 to 412 °C, which can be attributed to the loss of organic molecules (calcd 73.23%). The fluorescence of complex 1 was investigated because the introduction of d10 clusters can improve the fluorescence performance of MOFs. It can be observed that at room temperature, complex 1 exhibits fluorescence with emission maximum at 467 nm upon excitation at 349 nm. After removal

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Figure 6. The temperature dependence conductivity of complex 1.

of water molecules at 200 °C, the emission maximum adjusts to 493 nm (from blue to blue-green) and the intensity is enhanced about 1.5 times (Figure 5a). We can attribute the red-shift and the increase of emission intensity to the variation of the coordination environment. For complex 2, it exhibits an emission maximum 400 nm upon excitation at 323 nm as seen in Figure 5b. The above emissions can be assigned to the emission of ligand-to-metal charge transfer (LMCT).16 The conductivity of complex 1 was also investigated. As shown in Figure 6, the conductivity of complex 1 shows an electrical conductivity of 3.8  10-5 S cm-1 at 300 K and increases as temperature rises, which indicates that complex 1 is a semiconductor.17 However, the conductivity of complex 2 is in the range of 10-12 to 10-15 S cm-1 at room temperature, and independent of the temperature, which indicates it is an insulator. Through the comparison of the structures of 1 and 2, we can attribute the semiconductivity of 1 to the existence of Cd 3 3 3 Cd interactions in the octanuclear rod-shaped SBUs, which can further demonstrate the importance of high nuclear Cd clusters for the realization of multifunctionality of complex 1.

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Conclusion In summary, a unique 3D metal-organic framework built from octanuclear rod-shaped SBUs has been constructed. Complex 1 represents the first and only example of MOF built from high nuclear rod-shaped SBUs and also represents the biggest rod-shaped SBU based MOF of any known species. Furthermore, complex 1 exhibits interesting electrical conductivity and fluorescence properties. The successful synthesis of complex 1 provides a new number to the family of MOFs constructed from high-nuclear rod-shaped SBUs, which process excellent electrical and optical properties. Under about the same conditions, another new complex 2 has also been synthesized. Complex 2 exhibits a 2D supramolecular layer structure composed from 1D chains.

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Acknowledgment. We gratefully acknowledge the financial support from the Fundamental Research Funds for the Central Universities (N09035002) and the Postdoctoral station Foundation of North East University. Supporting Information Available: IR spectra of 1, 2 (Figure S1, S2), TGA curves of 1, 2 (Figure S3, S4), PXRD of 1, 2 (Figure S5, S6) in PDF format and crystallographic data in CIF format. This information is available free of charge via the Internet at http:// pubs.acs.org/.

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