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A 3-D bismuth–organic framework containing 1-D cationic inorganic [Bi2O2]2+ chains
Inorganic Chemistry Communications 12 (2009) 1081–1084
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
A 3-D bismuth–organic framework containing 1-D cationic inorganic [Bi2O2]2+ chains Dat T. Tran a,*, Deryn Chu a, Allen G. Oliver b, Scott R.J. Oliver b,* a b
U.S. Army Research Laboratory, Adelphi, MD 20783-1197, USA Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, CA 95064, USA
a r t i c l e
i n f o
Article history: Received 3 August 2009 Accepted 29 August 2009 Available online 4 September 2009 Keywords: Metal–organic framework Hydrothermal synthesis 3,5-Pyridinedicarboxylate 1-D bismuth oxide chains 1-D extended inorganic chains Bismuth–organic framework
a b s t r a c t A three-dimensional Bi(III) based metal–organic framework was synthesized under hydrothermal conditions using the multidentate organic linker 3,5-pyridinedicarboxylate. Bismuth oxide 3,5-pyridinedicarboxylate, Bi2O2[NC5H3(CO2)2], contains embedded 1-D cationic bismuth oxide chains that propagate along the crystallographic c-axis. The oxygens of the Bi2O2 core are three-coordinate and bond strongly to the Bi atoms. Thermogravimetric analysis shows that the material possesses high thermal stability up ca. 400 °C before decomposing to phase-pure Bi2O3 at 800 °C. The structure, crystallinity, morphology and properties of the material are discussed. Published by Elsevier B.V.
One of our research interests is the synthesis of metal–organic frameworks (MOFs) where extended inorganic 1-D chains [1] or 2-D layers [2] are embedded within the structure. Bismuth(III) complexes have recently gained traction in various applications including biological or medicinal [3–5], materials chemistry [6– 8], organic synthesis [9] and catalysis [10]. Bismuth is a p-block element and heavy metal that has a high affinity for O and N donor atoms of organic ligands to create stable complexes. Complexes are formed with a variety of species including aminoethanethiolate [11], xanthate, dithiocarbamate and phosphorous based ligands [7], just to name a few. For the past few years, the wide array of bismuth complexes have been reviewed exhaustively in the literature [3,6,7,9,10]. Bismuth(III) complexes and MOFs have been prepared by several different routes. To follows are a few examples. In 1984, Polla et al. synthesized bismuth oxalate single crystals, Bi2(C2O4)37H2O and Bi2(C2O4)3H2C2O4, using two different approaches, slow evaporation from solution and gel growth at room temperature [12]. Details of these structures in terms of molecular or extended structures were not studied. Last year, Rivenet et al. prepared single crystals of bismuth oxalate hydroxide [Bi(C2O4)OH], a 3-D metal– organic framework, in a silica gel medium at room temperature; they also formed a powder of the same material via aqueous solution titration under constant stirring at 50 °C [13]. Andrews et al.
* Corresponding authors. Tel.: +1 301 394 0293; fax: +1 301 394 0273 (D.T. Tran). E-mail address: [email protected] (D.T. Tran). 1387-7003/$ - see front matter Published by Elsevier B.V. doi:10.1016/j.inoche.2009.08.030
reported the synthesis of bismuth(III) carboxylates, molecular structures, using both solvent-free and reflux conditions [14]. Wullens et al. synthesized molecular solid heterodinuclear Bi–La and Bi–Pr complexes with polyaminocarboxylate ligands under stirring and heat [15]. Low-valent bismuth(II) carboxylate, 1-D polymeric structure, was also prepared using a solid solution of bismuth(0) and bismuth(III) trifluoroacetate in a sealed, evacuated glass ampule heated at 110 °C for 2 days [16]. In addition, many other bismuth complexes have been recently synthesized [17– 22], just to list a few. Bismuth based MOFs, however, are very scarce in the literature [13,23]. Despite the rich chemistry of bismuth complexes, most have very low thermal stability. This behavior is attributed to loss of water molecules (hydrated or free molecules) and decomposition of organic ligands within the structures at approximate temperatures of 100–300 °C, a range also often observed for MOFs. Furthermore, the lack of extended inorganic connectivity within the structures further contributes to the low thermal stability. To our knowledge, Bi(C2O4)OH is the only bismuth containing MOF that contains 1-D extended inorganic [BiO5E] chains, where E is a lone pair electron [13]. This material, however, showed a low temperature transition to metastable b-Bi2O3 at about 250 °C. We describe here the synthesis and characterization of a threedimensional Bi(III) based metal–organic framework, bismuth oxide 3,5-pyridinedicarboxylate (Bi2O2[NC5H3(CO2)2], which we denote ARL-3, for U.S. Army Research Laboratory, structure no. 3). The present compound contains 1-D cationic extended inorganic
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[Bi2O2]2+ chains linked into a 3-D bismuth–organic framework and was assembled under hydrothermal conditions using the organic linker 3,5-pyridinedicarboxylate (pdc) [24]. ARL-3 was synthesized by hydrothermal synthesis and formed in high yield at a range of synthesis temperatures (130, 165, and 200 °C). PXRD patterns of these crystal products are identical (Fig. S1a). The compound crystallizes with a colorless needle-like morphology (Fig. S2). Single crystals of suitable size were obtained for single crystal X-ray diffraction [25]. Detailed crystallographic data are given in Table S1 and selected bond lengths and angles are listed in Table S2. Though the structure is not chiral, it crystallizes in the acentric, orthorhombic space group Fdd2. The correct enantiomorph of the space group was determined by comparison of reflection intensities of Friedel pairs, giving a Flack parameter of 0.033(14). A value of zero indicates the correct absolute configuration. The compound forms a 3-D network with two crystallographically distinct Bi centers in the asymmetric unit (Fig. 1). 1-D cationic [Bi2O2]2+ chains run through the lattice parallel to the crystallographic c-axis (Fig. 2). The pyridine dicarboxylate moieties bridge these chains via Bi–carboxylate oxygen bonds, giving a 3-D network and overall formula Bi2O2[NC5H3(CO2)2]. Each pyridine dicarboxylate bonds to three different bismuthate chains (Fig. 3). Within the chains, O5 is three-coordinate while O6 is four coordinate, the former having somewhat shorter bonds to bismuth (Bi–O5: 2.117–2.270 Å; Bi–O6: 2.268–2.333 Å). The carboxylato oxygen (O1–O4) to Bi center distances range from 2.313 to 2.730 Å. O4 forms a weaker interaction of 2.806 Å to Bi2; this distance is just outside the contact range assumed for bonding and is thus a long contact. The pyridine nitrogen also has a long contact to the nearby Bi(2) atom (N–Bi: 2.851(7) Å), again likely to be a real, if weaker, contact. Both Bi(1)O5 and Bi(2)O4N centers possess an umbrella-like geometry typical of lower p-block metals. Thermogravimetric analysis (TGA) shows that the ARL-3 material is stable to ca. 400 °C (Fig. S3), significantly higher than that observed for bismuth based MOF [Bi(C2O4)OH] at 250 °C. This high thermal stability of the material is due to strong covalent bonds between Bi centers to oxygens within the 1-D cationic extended
Fig. 1. ORTEP diagram and atom labeling scheme for ARL-3.
Fig. 2. Crystallographic a-projection (Bi: green; O: red; N: blue; C: gray; H atoms omitted for clarity), showing 1-D [Bi2O2]+2 chains. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
inorganic [Bi2O2]2+ chains, and Bi centers to oxygens of the pdc ligands. The trace displays one major thermal event. The mass loss of about 27.2% in the region of 400–800 °C is attributed to the removal of the pdc ligands (expected: 26.8%). The PXRD pattern after heating the material to 800 °C (Fig. S1b) reveals that the material collapses to phase-pure Bi2O3 (ICDD #00-041-1449). The high thermal stability of the compound is likely due to the embedded [Bi2O2]2+ chains within the lattice structure as well as high overall dimensionality of the MOF. MOFs with extended inorganic 1-D chains or 2-D layers implanted within the structure was carefully reviewed by Cheetham et al. [27] and we have previously reported several such structures previously based on Cu [1,2] and Pb [28]. In summary, we have successfully prepared a 3-D bismuth–organic compound hydrothermally. ARL-3 is stable to ca. 400 °C, which represents far greater thermal stability over previously reported bismuth based MOF stable to 250 °C [13]. The new 3-D metal–organic framework consists of 1-D extended inorganic [Bi2O2]2+ chains entrenched within the 3-D bismuth–organic framework. The oxygens of the Bi2O2 core are three-coordinate centers and are very tightly bonded to the Bi atoms. Thermal data indicate transformation to a known phase Bi2O3 at 800 °C. We are currently working toward materials with higher inorganic dimensionality embedded within the MOF structure for further improved stability.
D.T. Tran et al. / Inorganic Chemistry Communications 12 (2009) 1081–1084
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Fig. 3. Crystallographic c-projection of one layer, showing the 3-D bismuth–organic connectivity. These chains are seen end-on.
Acknowledgments The Army Research Laboratory is acknowledged for financial support of this research. S.O. acknowledges financial support from an NSF Career Award (DMR-0506279). Samples for synchrotron crystallographic analysis were submitted through the SCrALS (Service Crystallography at Advanced Light Source) program. The ALS is supported by the US Department of Energy, Office of Energy Sciences, under contract DE-AC02-05CH11231. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2009.08.030. References [1] D.T. Tran, X.-J. Fan, D.P. Brennan, P.Y. Zavalij, S.R.J. Oliver, Inorg. Chem. 44 (2005) 6192–6196. [2] D.T. Tran, N.A. Chernova, D. Chu, A.G. Oliver, S.R.J. Oliver, Manuscript, submitted for publication. [3] G.G. Briand, N. Burford, Chem. Rev. 99 (1999) 2601–2657. [4] D.E. Mahony, S. Lim-Morrison, L. Bryden, G. Faulkner, P.S. Hoffman, L. Agocs, G.G. Briand, N. Burford, H. Maguire, Antimicrob. Agents Chemother. 43 (1999) 582–588. [5] E. Csajbok, Z. Baranyai, I. Banyai, E. Brucher, R. Kiraly, A. Muller-Fahrnow, J. Platzek, B. Raduchel, M. Schafer, Inorg. Chem. 42 (2003) 2342–2349. [6] V. Stavila, R.L. Davidovich, A. Gulea, K.H. Whitmire, Coord. Chem. Rev. 250 (2006) 2782–2810. [7] S.S. Garje, V.K. Jain, Coord. Chem. Rev. 236 (2003) 35–56. [8] M. Devillers, O. Tirions, L. Cadus, P. Ruiz, B. Delmon, J. Solid State Chem. 126 (1996) 152–160. [9] N.M. Leonard, L.C. Wieland, R.S. Mohan, Tetrahedron 58 (2002) 8373–8397. [10] T.A. Hanna, Coord. Chem. Rev. 248 (2004) 429–440. [11] G.G. Briand, N. Burford, T.S. Cameron, W. Kwiatkowski, J. Am. Chem. Soc. 120 (1998) 11374–11379. [12] G. Polla, R.F. Baggio, E. Manghi, P.K. De Perazzo, J. Cryst. Growth 67 (1984) 68– 74. [13] M. Rivenet, P. Roussel, F. Abraham, J. Solid State Chem. 181 (2008) 2586–2590.
[14] P.C. Andrews, G.B. Deacon, P.C. Junk, I. Kumar, M. Silberstein, Dalton Trans. (2006) 4852–4858. [15] H. Wullens, N. Bodart, M. Devillers, J. Solid State Chem. 167 (2002) 494–507. [16] E.V. Dikarev, B. Li, Inorg. Chem. 43 (2004) 3461–3466. [17] J. Reglinski, M.D. Spicer, M. Garner, A.R. Kennedy, J. Am. Chem. Soc. 121 (1999) 2317–2318. [18] G.G. Briand, N. Burford, M.D. Eelman, T.S. Cameron, K.N. Robertson, Inorg. Chem. 42 (2003) 3136–3141. [19] G.G. Briand, N. Burford, M.D. Eelman, N. Aumeerally, L. Chen, T.S. Cameron, K.N. Robertson, Inorg. Chem. 43 (2004) 6495–6500. [20] V. Stavila, J.C. Fettinger, K.H. Whitmire, Organometallics 26 (2007) 3321–3328. [21] V. Stavila, J.H. Thurston, D. Prieto-Centurion, K.H. Whitmire, Organometallics 26 (2007) 6864–6866. [22] L. Liu, L.N. Zakharov, J.A. Golen, A.L. Rheingold, T.A. Hanna, Inorg. Chem. 47 (2008) 11143–11153. [23] R. Kumar, P. Mishra, Main Group Chem. 6 (2007) 85–95. [24] Bismuth oxide 3,5-pyridinedicarboxylate, Bi2O2[NC5H3(CO2)2], was prepared in a simple, one-step reaction. The as-synthesized material formed under hydrothermal conditions at 165 °C for 3 days, in which the final reaction mixture had a molar ratio of 575 H2O:1.0 Bi(NO3)35H2O:0.48 3,5pyridinedicarboxylic acid (pdc). All chemicals were purchased and used asreceived. In a typical reaction, 32.0 mL of deionized H2O, 1.5 g of Bi(NO3)35H2O (Aldrich, 98+%) and 0.25 g of pdc (Matrix Scientific, 95%) were added to a Nalgene beaker. After ca. 15 min. stirring, the solution was transferred to a 45 mL capacity Teflon-lined stainless steel autoclave. The autoclave was sealed and heated at 130 to 200 °C for 3 days. The crystals were collected by vacuum filtration, rinsed with deionized water and allowed to airdry overnight. The crystal product from 130 °C weighed ca. 770 mg (yield: 83.7%). The crystal product from 165 °C weighed ca. 790 mg (yield: 85.9%), while the 200 °C product yielded a total of 809 mg (yield: 87.9%). Elemental analysis (Galbraith Laboratories Inc., Knoxville, TN) agrees well with the structural formula. Analyzed percentages of C, H and N were 9.39%, < 0.5% and 2.28%, compared with 13.6%, 0.48% and 2.28% calculated from the structure solution, respectively. [25] A fragment of a colorless block-like crystal of Bi2O2[NC5H3(CO2)2] having approximate dimensions of 0.08 0.07 0.05 mm was mounted on a Kapton loop using Paratone N hydrocarbon oil. All measurements were collected on a Bruker APEX-II [26a] CCD area detector with channel-cut Si-h111i crystal monochromated synchrotron radiation. Crystallographic data were collected at Beamline 11.3.1 at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory (k = 0.77490 Å). The data were collected at a temperature of 150(2) K giving l(Mo-Ka) = 39.978 mm1, R1 = 0.0294, wR2 = 0.0648 for 1848 data with I > 2r(I) and R1 = 0.0306, wR2 = 0.0654 for all 1919 data. Frames corresponding to an arbitrary sphere of data were collected using xscans of 0.3° counted for a total of 1 s per frame. Data were integrated by the
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program SAINT [26b] to a maximum h-value of 31.07°. The data were corrected for Lorentz and polarization effects, then analyzed for agreement and possible absorption using XPREP [26c]. An empirical absorption correction based on comparison of redundant and equivalent reflections was applied using SADABS [26d]. The structure was solved by direct methods [26e] and expanded using Fourier techniques [26f]. [26] (a) APEX-II: Area-Detector Software Package v2.1, Bruker Analytical X-ray Systems Inc., Madison, WI, 2006.; (b) SAINT: SAX Area-Detector Integration Program, 7.34 , Siemens Industrial Automation Inc., Madison, WI, 2006.; (c) XPREP: (v 6.14) Part of the SHELXTL Crystal Structure Determination Package, Siemens Industrial Automation Inc., Madison, WI, 1995.;
(d) SADABS: Siemens Area Detector Absorption correction Program v.2.10, George Sheldrick, 2005.; (e) XS: Program for the Solution of X-ray Crystal Structures, Part of the SHELXTL Crystal Structure Determination Package, Bruker Analytical X-ray Systems Inc., Madison, WI, 1995–99.; (f) XL: Program for the Refinement of X-ray Crystal Structure, Part of the SHELXTL Crystal Structure Determination Package, Bruker Analytical X-ray Systems Inc., Madison, WI, 1995–99. [27] A.K. Cheetham, C.N.R. Rao, R.K. Feller, Chem. Commun. (2006) 4780–4795. [28] D.L. Rogow, G. Zapeda, C.H. Swanson, X. Fan, A.G. Oliver, S.R.J. Oliver, Chem. Mater. 19 (2007) 4658–4662.
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
A 3-D bismuth–organic framework containing 1-D cationic inorganic [Bi2O2]2+ chains Dat T. Tran a,*, Deryn Chu a, Allen G. Oliver b, Scott R.J. Oliver b,* a b
U.S. Army Research Laboratory, Adelphi, MD 20783-1197, USA Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, CA 95064, USA
a r t i c l e
i n f o
Article history: Received 3 August 2009 Accepted 29 August 2009 Available online 4 September 2009 Keywords: Metal–organic framework Hydrothermal synthesis 3,5-Pyridinedicarboxylate 1-D bismuth oxide chains 1-D extended inorganic chains Bismuth–organic framework
a b s t r a c t A three-dimensional Bi(III) based metal–organic framework was synthesized under hydrothermal conditions using the multidentate organic linker 3,5-pyridinedicarboxylate. Bismuth oxide 3,5-pyridinedicarboxylate, Bi2O2[NC5H3(CO2)2], contains embedded 1-D cationic bismuth oxide chains that propagate along the crystallographic c-axis. The oxygens of the Bi2O2 core are three-coordinate and bond strongly to the Bi atoms. Thermogravimetric analysis shows that the material possesses high thermal stability up ca. 400 °C before decomposing to phase-pure Bi2O3 at 800 °C. The structure, crystallinity, morphology and properties of the material are discussed. Published by Elsevier B.V.
One of our research interests is the synthesis of metal–organic frameworks (MOFs) where extended inorganic 1-D chains [1] or 2-D layers [2] are embedded within the structure. Bismuth(III) complexes have recently gained traction in various applications including biological or medicinal [3–5], materials chemistry [6– 8], organic synthesis [9] and catalysis [10]. Bismuth is a p-block element and heavy metal that has a high affinity for O and N donor atoms of organic ligands to create stable complexes. Complexes are formed with a variety of species including aminoethanethiolate [11], xanthate, dithiocarbamate and phosphorous based ligands [7], just to name a few. For the past few years, the wide array of bismuth complexes have been reviewed exhaustively in the literature [3,6,7,9,10]. Bismuth(III) complexes and MOFs have been prepared by several different routes. To follows are a few examples. In 1984, Polla et al. synthesized bismuth oxalate single crystals, Bi2(C2O4)37H2O and Bi2(C2O4)3H2C2O4, using two different approaches, slow evaporation from solution and gel growth at room temperature [12]. Details of these structures in terms of molecular or extended structures were not studied. Last year, Rivenet et al. prepared single crystals of bismuth oxalate hydroxide [Bi(C2O4)OH], a 3-D metal– organic framework, in a silica gel medium at room temperature; they also formed a powder of the same material via aqueous solution titration under constant stirring at 50 °C [13]. Andrews et al.
* Corresponding authors. Tel.: +1 301 394 0293; fax: +1 301 394 0273 (D.T. Tran). E-mail address: [email protected] (D.T. Tran). 1387-7003/$ - see front matter Published by Elsevier B.V. doi:10.1016/j.inoche.2009.08.030
reported the synthesis of bismuth(III) carboxylates, molecular structures, using both solvent-free and reflux conditions [14]. Wullens et al. synthesized molecular solid heterodinuclear Bi–La and Bi–Pr complexes with polyaminocarboxylate ligands under stirring and heat [15]. Low-valent bismuth(II) carboxylate, 1-D polymeric structure, was also prepared using a solid solution of bismuth(0) and bismuth(III) trifluoroacetate in a sealed, evacuated glass ampule heated at 110 °C for 2 days [16]. In addition, many other bismuth complexes have been recently synthesized [17– 22], just to list a few. Bismuth based MOFs, however, are very scarce in the literature [13,23]. Despite the rich chemistry of bismuth complexes, most have very low thermal stability. This behavior is attributed to loss of water molecules (hydrated or free molecules) and decomposition of organic ligands within the structures at approximate temperatures of 100–300 °C, a range also often observed for MOFs. Furthermore, the lack of extended inorganic connectivity within the structures further contributes to the low thermal stability. To our knowledge, Bi(C2O4)OH is the only bismuth containing MOF that contains 1-D extended inorganic [BiO5E] chains, where E is a lone pair electron [13]. This material, however, showed a low temperature transition to metastable b-Bi2O3 at about 250 °C. We describe here the synthesis and characterization of a threedimensional Bi(III) based metal–organic framework, bismuth oxide 3,5-pyridinedicarboxylate (Bi2O2[NC5H3(CO2)2], which we denote ARL-3, for U.S. Army Research Laboratory, structure no. 3). The present compound contains 1-D cationic extended inorganic
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[Bi2O2]2+ chains linked into a 3-D bismuth–organic framework and was assembled under hydrothermal conditions using the organic linker 3,5-pyridinedicarboxylate (pdc) [24]. ARL-3 was synthesized by hydrothermal synthesis and formed in high yield at a range of synthesis temperatures (130, 165, and 200 °C). PXRD patterns of these crystal products are identical (Fig. S1a). The compound crystallizes with a colorless needle-like morphology (Fig. S2). Single crystals of suitable size were obtained for single crystal X-ray diffraction [25]. Detailed crystallographic data are given in Table S1 and selected bond lengths and angles are listed in Table S2. Though the structure is not chiral, it crystallizes in the acentric, orthorhombic space group Fdd2. The correct enantiomorph of the space group was determined by comparison of reflection intensities of Friedel pairs, giving a Flack parameter of 0.033(14). A value of zero indicates the correct absolute configuration. The compound forms a 3-D network with two crystallographically distinct Bi centers in the asymmetric unit (Fig. 1). 1-D cationic [Bi2O2]2+ chains run through the lattice parallel to the crystallographic c-axis (Fig. 2). The pyridine dicarboxylate moieties bridge these chains via Bi–carboxylate oxygen bonds, giving a 3-D network and overall formula Bi2O2[NC5H3(CO2)2]. Each pyridine dicarboxylate bonds to three different bismuthate chains (Fig. 3). Within the chains, O5 is three-coordinate while O6 is four coordinate, the former having somewhat shorter bonds to bismuth (Bi–O5: 2.117–2.270 Å; Bi–O6: 2.268–2.333 Å). The carboxylato oxygen (O1–O4) to Bi center distances range from 2.313 to 2.730 Å. O4 forms a weaker interaction of 2.806 Å to Bi2; this distance is just outside the contact range assumed for bonding and is thus a long contact. The pyridine nitrogen also has a long contact to the nearby Bi(2) atom (N–Bi: 2.851(7) Å), again likely to be a real, if weaker, contact. Both Bi(1)O5 and Bi(2)O4N centers possess an umbrella-like geometry typical of lower p-block metals. Thermogravimetric analysis (TGA) shows that the ARL-3 material is stable to ca. 400 °C (Fig. S3), significantly higher than that observed for bismuth based MOF [Bi(C2O4)OH] at 250 °C. This high thermal stability of the material is due to strong covalent bonds between Bi centers to oxygens within the 1-D cationic extended
Fig. 1. ORTEP diagram and atom labeling scheme for ARL-3.
Fig. 2. Crystallographic a-projection (Bi: green; O: red; N: blue; C: gray; H atoms omitted for clarity), showing 1-D [Bi2O2]+2 chains. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
inorganic [Bi2O2]2+ chains, and Bi centers to oxygens of the pdc ligands. The trace displays one major thermal event. The mass loss of about 27.2% in the region of 400–800 °C is attributed to the removal of the pdc ligands (expected: 26.8%). The PXRD pattern after heating the material to 800 °C (Fig. S1b) reveals that the material collapses to phase-pure Bi2O3 (ICDD #00-041-1449). The high thermal stability of the compound is likely due to the embedded [Bi2O2]2+ chains within the lattice structure as well as high overall dimensionality of the MOF. MOFs with extended inorganic 1-D chains or 2-D layers implanted within the structure was carefully reviewed by Cheetham et al. [27] and we have previously reported several such structures previously based on Cu [1,2] and Pb [28]. In summary, we have successfully prepared a 3-D bismuth–organic compound hydrothermally. ARL-3 is stable to ca. 400 °C, which represents far greater thermal stability over previously reported bismuth based MOF stable to 250 °C [13]. The new 3-D metal–organic framework consists of 1-D extended inorganic [Bi2O2]2+ chains entrenched within the 3-D bismuth–organic framework. The oxygens of the Bi2O2 core are three-coordinate centers and are very tightly bonded to the Bi atoms. Thermal data indicate transformation to a known phase Bi2O3 at 800 °C. We are currently working toward materials with higher inorganic dimensionality embedded within the MOF structure for further improved stability.
D.T. Tran et al. / Inorganic Chemistry Communications 12 (2009) 1081–1084
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Fig. 3. Crystallographic c-projection of one layer, showing the 3-D bismuth–organic connectivity. These chains are seen end-on.
Acknowledgments The Army Research Laboratory is acknowledged for financial support of this research. S.O. acknowledges financial support from an NSF Career Award (DMR-0506279). Samples for synchrotron crystallographic analysis were submitted through the SCrALS (Service Crystallography at Advanced Light Source) program. The ALS is supported by the US Department of Energy, Office of Energy Sciences, under contract DE-AC02-05CH11231. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2009.08.030. References [1] D.T. Tran, X.-J. Fan, D.P. Brennan, P.Y. Zavalij, S.R.J. Oliver, Inorg. Chem. 44 (2005) 6192–6196. [2] D.T. Tran, N.A. Chernova, D. Chu, A.G. Oliver, S.R.J. Oliver, Manuscript, submitted for publication. [3] G.G. Briand, N. Burford, Chem. Rev. 99 (1999) 2601–2657. [4] D.E. Mahony, S. Lim-Morrison, L. Bryden, G. Faulkner, P.S. Hoffman, L. Agocs, G.G. Briand, N. Burford, H. Maguire, Antimicrob. Agents Chemother. 43 (1999) 582–588. [5] E. Csajbok, Z. Baranyai, I. Banyai, E. Brucher, R. Kiraly, A. Muller-Fahrnow, J. Platzek, B. Raduchel, M. Schafer, Inorg. Chem. 42 (2003) 2342–2349. [6] V. Stavila, R.L. Davidovich, A. Gulea, K.H. Whitmire, Coord. Chem. Rev. 250 (2006) 2782–2810. [7] S.S. Garje, V.K. Jain, Coord. Chem. Rev. 236 (2003) 35–56. [8] M. Devillers, O. Tirions, L. Cadus, P. Ruiz, B. Delmon, J. Solid State Chem. 126 (1996) 152–160. [9] N.M. Leonard, L.C. Wieland, R.S. Mohan, Tetrahedron 58 (2002) 8373–8397. [10] T.A. Hanna, Coord. Chem. Rev. 248 (2004) 429–440. [11] G.G. Briand, N. Burford, T.S. Cameron, W. Kwiatkowski, J. Am. Chem. Soc. 120 (1998) 11374–11379. [12] G. Polla, R.F. Baggio, E. Manghi, P.K. De Perazzo, J. Cryst. Growth 67 (1984) 68– 74. [13] M. Rivenet, P. Roussel, F. Abraham, J. Solid State Chem. 181 (2008) 2586–2590.
[14] P.C. Andrews, G.B. Deacon, P.C. Junk, I. Kumar, M. Silberstein, Dalton Trans. (2006) 4852–4858. [15] H. Wullens, N. Bodart, M. Devillers, J. Solid State Chem. 167 (2002) 494–507. [16] E.V. Dikarev, B. Li, Inorg. Chem. 43 (2004) 3461–3466. [17] J. Reglinski, M.D. Spicer, M. Garner, A.R. Kennedy, J. Am. Chem. Soc. 121 (1999) 2317–2318. [18] G.G. Briand, N. Burford, M.D. Eelman, T.S. Cameron, K.N. Robertson, Inorg. Chem. 42 (2003) 3136–3141. [19] G.G. Briand, N. Burford, M.D. Eelman, N. Aumeerally, L. Chen, T.S. Cameron, K.N. Robertson, Inorg. Chem. 43 (2004) 6495–6500. [20] V. Stavila, J.C. Fettinger, K.H. Whitmire, Organometallics 26 (2007) 3321–3328. [21] V. Stavila, J.H. Thurston, D. Prieto-Centurion, K.H. Whitmire, Organometallics 26 (2007) 6864–6866. [22] L. Liu, L.N. Zakharov, J.A. Golen, A.L. Rheingold, T.A. Hanna, Inorg. Chem. 47 (2008) 11143–11153. [23] R. Kumar, P. Mishra, Main Group Chem. 6 (2007) 85–95. [24] Bismuth oxide 3,5-pyridinedicarboxylate, Bi2O2[NC5H3(CO2)2], was prepared in a simple, one-step reaction. The as-synthesized material formed under hydrothermal conditions at 165 °C for 3 days, in which the final reaction mixture had a molar ratio of 575 H2O:1.0 Bi(NO3)35H2O:0.48 3,5pyridinedicarboxylic acid (pdc). All chemicals were purchased and used asreceived. In a typical reaction, 32.0 mL of deionized H2O, 1.5 g of Bi(NO3)35H2O (Aldrich, 98+%) and 0.25 g of pdc (Matrix Scientific, 95%) were added to a Nalgene beaker. After ca. 15 min. stirring, the solution was transferred to a 45 mL capacity Teflon-lined stainless steel autoclave. The autoclave was sealed and heated at 130 to 200 °C for 3 days. The crystals were collected by vacuum filtration, rinsed with deionized water and allowed to airdry overnight. The crystal product from 130 °C weighed ca. 770 mg (yield: 83.7%). The crystal product from 165 °C weighed ca. 790 mg (yield: 85.9%), while the 200 °C product yielded a total of 809 mg (yield: 87.9%). Elemental analysis (Galbraith Laboratories Inc., Knoxville, TN) agrees well with the structural formula. Analyzed percentages of C, H and N were 9.39%, < 0.5% and 2.28%, compared with 13.6%, 0.48% and 2.28% calculated from the structure solution, respectively. [25] A fragment of a colorless block-like crystal of Bi2O2[NC5H3(CO2)2] having approximate dimensions of 0.08 0.07 0.05 mm was mounted on a Kapton loop using Paratone N hydrocarbon oil. All measurements were collected on a Bruker APEX-II [26a] CCD area detector with channel-cut Si-h111i crystal monochromated synchrotron radiation. Crystallographic data were collected at Beamline 11.3.1 at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory (k = 0.77490 Å). The data were collected at a temperature of 150(2) K giving l(Mo-Ka) = 39.978 mm1, R1 = 0.0294, wR2 = 0.0648 for 1848 data with I > 2r(I) and R1 = 0.0306, wR2 = 0.0654 for all 1919 data. Frames corresponding to an arbitrary sphere of data were collected using xscans of 0.3° counted for a total of 1 s per frame. Data were integrated by the
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program SAINT [26b] to a maximum h-value of 31.07°. The data were corrected for Lorentz and polarization effects, then analyzed for agreement and possible absorption using XPREP [26c]. An empirical absorption correction based on comparison of redundant and equivalent reflections was applied using SADABS [26d]. The structure was solved by direct methods [26e] and expanded using Fourier techniques [26f]. [26] (a) APEX-II: Area-Detector Software Package v2.1, Bruker Analytical X-ray Systems Inc., Madison, WI, 2006.; (b) SAINT: SAX Area-Detector Integration Program, 7.34 , Siemens Industrial Automation Inc., Madison, WI, 2006.; (c) XPREP: (v 6.14) Part of the SHELXTL Crystal Structure Determination Package, Siemens Industrial Automation Inc., Madison, WI, 1995.;
(d) SADABS: Siemens Area Detector Absorption correction Program v.2.10, George Sheldrick, 2005.; (e) XS: Program for the Solution of X-ray Crystal Structures, Part of the SHELXTL Crystal Structure Determination Package, Bruker Analytical X-ray Systems Inc., Madison, WI, 1995–99.; (f) XL: Program for the Refinement of X-ray Crystal Structure, Part of the SHELXTL Crystal Structure Determination Package, Bruker Analytical X-ray Systems Inc., Madison, WI, 1995–99. [27] A.K. Cheetham, C.N.R. Rao, R.K. Feller, Chem. Commun. (2006) 4780–4795. [28] D.L. Rogow, G. Zapeda, C.H. Swanson, X. Fan, A.G. Oliver, S.R.J. Oliver, Chem. Mater. 19 (2007) 4658–4662.