A Chemically Functionalizable Nanoporous Material [Cu 3 (TMA) 2 (H 2 O) 3 ] n

American Association for the Advancement of Science (AAAS) - Tập 283 Số 5405 - Trang 1148-1150 - 1999
S.S.-Y. Chui1, S.M.F. Lo1, J.P.H. Charmant2, A. Guy Orpen2, Ian D. Williams1
1Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
2School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK

Tóm tắt

Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu 3 (TMA) 2 (H 2 O) 3 ] n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu 2 (O 2 CR) 4 ] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240°C.

Từ khóa


Tài liệu tham khảo

10.1126/science.278.5346.2080

10.1021/ar00027a006

; O. E. Akporiaye J. Chem. Soc. Chem. Commun. 1994 1711 (1994);

10.1038/367347a0

Feng P., Bu X., Tolbert S. H., Stucky G. D., J. Am. Chem. Soc. 119, 24987 (1997).

10.1021/ja00368a062

10.1038/41937

10.1038/369727a0

10.1021/ja00082a055

10.1038/378703a0

10.1021/ja9639473

10.1039/C39900001677

10.1002/anie.199416651

10.1021/ja00121a014

10.1038/374792a0

10.1021/ja00124a032

; B. F. Abrahams S. R. Batten H. Hamit B. F. Hoskins R. Robson Chem. Commun. 1996 1313 (1996);

Blake A. J., et al., ibid. 1997, 1005 (1997);

; A. J. Blake et al. ibid. p. 2027; C. J. Kepert and M. J. Rosseinsky ibid. 1998 31 (1998).

10.1002/anie.199521271

Pech R., Pickardt J., Acta Crystallogr. C44, 992 (1988).

Chui S. S.-Y., Williams I. D., ibid. C55, 194 (1999).

10.1039/cc9960000823

Crystals of [Mn(TMA-H 2 ) 2 (H 2 O) 4 ] were formed by layer diffusion of ethanolic [TMA-H 3 ] into aqueous Mn(OAc) 2 at RT. The monoclinic crystal system data are as follows: unit cell edges are a = 5.178(2) Å b = 13.127(3) Å and c = 15.142(3) Å; interaxial angle β = 97.74(2)°; and cell volume V = 1019(1) Å 3 .

In a typical synthesis 1.8 mM of cupric nitrate trihydrate was heated with 1.0 mM of trimesic acid (TMA-H 3 ) in 12 ml of 50:50 H 2 O:EtOH (EtOH ethyl alcohol) at 180°C for 12 hours in a Teflon-lined 23-ml Parr pressure vessel. This gave turquoise crystals up to dimensions of 80 μm in ∼60% yield along with Cu metal and Cu 2 O. Single-crystal x-ray analysis of the turquoise crystals (HKUST-1) was carried out with a Siemens diffractometer that was equipped with a SMART charge-coupled device.

Crystal data for HKUST-1 were measured as follows: C 18 H 12 O 15 Cu 3 relative molecular mass M r = 658.9 cubic crystal system space group Fm - 3m a = 26.343(5) Å V = 18 280(7) Å 3 formula units per cell Z = 16 density D x = 0.96 g cm –3 conventional discrepancy index R = 5.99 and weighted wR2 = 16.78; for 43 least-squares parameters and 853 reflections diffraction angle 2Θmax = 50°. The structure was refined with SHELXL. A full description of the x-ray analysis is available at www.sciencemag.org/feature/data/986116.shl. The coordinates are on deposit with the Cambridge Structural Database deposit number 112954.

10.1107/S0567740874008053

Brignole A. B., Cotton F. A., Inorg. Synth. 13, 81 (1972).

10.1016/S0040-4020(01)89741-6

D. W. Breck Zeolite Molecular Sieves (Kreiger Malabar FL 1974) p. 48; ibid. p. 625. The BET data are available at www.sciencemag.org/feature/data/986116.shl.

10.1002/(SICI)1521-3773(19980817)37:15<2082::AID-ANIE2082>3.0.CO;2-0

10.1246/bcsj.69.1471

10.1002/anie.199616901

Lattice expansion occurred in a family of Cu polymers containing N N′ donor bridges [

10.1021/ic9603520

; S. Kitagawa paper presented at the 1st International Conference on Inorganic Materials Versailles 16 to 19 September 1998].

10.1021/ja981669x

TGA results for HKUST-1 gave weight loss Δ w = –28.2% from 25° to 120°C (–13 H 2 O) thermal stability from 120°C to 250°C and Δ w = –25.4% from 250° to 400°C (–CO 2 and others). Further heating to 800°C resulted in a mixture of CuO and glassy C as final products. TGA curves are available at www.sciencemag.org/feature/data/986116.shl.

The analytical and calculated (in parentheses) data for [Cu 3 (TMA) 2 (py) 3 ]·0.5(py)·2H 2 O are as follows: C 43.54% (46.48%); H 3.54% (3.01%); and N 5.52% (5.30%). TGA showed Δ w = –3.9% from 25° to 120°C and Δ w = –54.2% from 120° to 400°C (–py –CO 2 and others).

A 2D network polymer [Cu 3 (TMA) 2 (py) 9 ]·3(py)·3H 2 O (space group R-3c a = 19.142(5) Å c = 42.64(1) Å and V = 13 532 Å 3 ) was formed with large 48-membered rings of six individual Cu atoms and six TMA groups.

Analysis for the DMF product gave the best formulation as [Cu 3 (TMA) 2 (H 2 O) 3 ]·2.5(DMF)·2.5(H 2 O) on the basis of combined chemical and thermal gravimetric analyses. The analytical and calculated (in parentheses) data are as follows: C 34.6% (34.5%); H 3.42% (3.89%); N 4.01% (3.95%); Δ w = –11.4% from 25° to 120°C (H 2 O loss); and Δ w = –48.6% from 150° to 400°C (DMF and CO 2 loss). Variable-temperature single-crystal studies of the DMSO derivative showed no bound DMSO at RT; heating up to 200°C produced intensity changes due to solvent loss (reflection 222 increases in intensity and reflection 400 decreases). Cooling to RT resulted in a general reversal of these trends.

Anhydrous [Er(TMA)] was synthesized hydrothermally at 180°C in a manner similar to the synthesis of HKUST-1; TGA under N 2 produced Δ w = < –1% from 25° to 500°C and Δ w = –45.7% from 500° to 650°C corresponding to decarboxylation.

We are grateful to the Research Grants Council of Hong Kong (RGC grants 6148-97P and 6061-98P) and the Advanced Materials Research Institute (AMRI-HKUST) for financial support and to J. Zheng and A. Siu for technical assistance.