REPORTS

Cu21 ions of the formula unit. Each metal

A Chemically Functionalizable completes its pseudooctahedral coordination
sphere with an axial aqua ligand opposite to the

Nanoporous Material Cu-Cu vector. Such bimetallic tetracarboxylate

units are a common and often highly stable

[Cu3(TMA)2(H2O)3]n
arrangement found not just for Cu but also for
many other transition metal carboxylates. Ex-
amples include the quadruply-bonded Mo
Stephen S.-Y. Chui,1 Samuel M.-F. Lo,1 Jonathan P. H. Charmant,2 dimers such as [Mo2(O2CCH3)4] (14) and its
A. Guy Orpen,2 Ian D. Williams1* catalytically active Rh analog [Rh2(O2CCH3)4]
(15). Several hundred such complexes have
Although zeolites and related materials combine nanoporosity with high ther- been crystallographically characterized, with a
mal stability, they are difficult to modify or derivatize in a systematic way. A wide variety of metals, carboxylate bridges, and
highly porous metal coordination polymer [Cu3( TMA)2(H2O)3]n (where TMA is axial ligands.
benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has intercon- A view down the [100] direction of the
nected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three- cubic cell of HKUST-1 reveals ;1-nm-size
dimensional system of channels with a pore size of 1 nanometer and an channels with fourfold symmetry (Fig. 2).
accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel Using the atomic centers of carboxylate oxy-
linings can be chemically functionalized; for example, the aqua ligands can be gens as the points of a square, we measured
replaced by pyridines. Thermal gravimetric analysis and high-temperature sin- the edge of the “square” as 9.5 or 13.3 Å
gle-crystal diffractometry indicate that the framework is stable up to 240°C. across its diagonal. The nanochannels inter-
sect to provide a 3D connected network of

Downloaded from http://science.sciencemag.org/ on March 20, 2018

Nanoporous materials that are based on The pores themselves contain up to 10 pores. A view through the cell body diagonal
zeolites and metal phosphates have found a additional water molecules per formula [111] reveals a honeycomb arrangement of
wide range of technological applications unit. The material has a reasonable degree large hexagonal-shaped windows (Fig. 3),
(for example, acting as molecular sieves, of thermal stability (up to 240°C) and a each composed of a ring of six metal dimers
desiccants, ion exchangers, and catalysts). capacity for chemical functionalization of and six trimesate groups, which measure 18.6
Although chemically and thermally stable, the channel linings. Å between opposite vertices. These windows
these materials create challenges to the en- The control of dimensionality is a major are cross sections of the “cavities” formed at
gineering of specific pore sizes (1) or to the challenge within the metal coordination poly- the intersection of the three orthogonal sets of
formation of chiral channels (2) and allow a mer field. Even when polyfunctional ligands channels.
rather limited variation of chemical formu- are used, ancillary ligation by water or other The experimentally determined absorp-
lation and functionality (3). The relatively solvent ligands may result in low dimensional- tion properties of HKUST-1 that was pre-
new field of microporous metallo-organic ity. In the case of Cu and trimesic acid [ben- treated by heating in a vacuum are consistent
polymers (4 –7 ), although offering great zene-1,3,5-tricarboxylic acid (TMA-H3)], one- with the high porosity indicated by its crystal
potential for chemical and structural diver- dimensional chain polymers [Cu(TMA-H)- structure. A N2 adsorption/desorption iso-
sity and including the direct incorporation (H2O)3]n (8) or [NaCu(TMA)(H2O)5] (9) form therm study gave the following values:
of catalytic sites, (4) suffers from general from alcoholic solutions of cupric ions and Brunauer-Emmett-Teller (BET) surface ar-
difficulties in the control of polymer di- trimesic acid at room temperature (RT). The ea 5 692.2 m2 g–1, Langmuir surface area 5
mensionality or framework stability. Low- low dimensionality is caused by the ligation of 917.6 m2 g–1, and single-point total pore
dimensional coordination polymers can three aqua groups per square-pyramidal Cu21 volume 5 0.333 cm3 g–1. Using a calculated
still show selective absorption based on ion. density of 1.22 g cm–3, we found that the
guest-host shape recognition (5), but they For entropic reasons, synthesis at a higher accessible porosity is 40.7% (that is, the void
lack framework integrity. Furthermore, al- temperature can promote the formation of poly- fraction is 0.41). This value compares favor-
though ligands can be designed to create mer frameworks of higher dimensionality ably with the void fractions (0.47 to 0.50) of
large voids, the resulting coordination through the loss of terminal ancillary ligands. the most open zeolites, such as the faujasite,
polymers are frequently plagued by lattice Thus, for example, Wood et al. (10) have found paulingite, and zeolite A families (16).
interpenetration (6 ) or a framework break- a condensed 3D structure for [Mn(TMA)], The tetracarboxylate unit provides a struc-
down upon the removal of absorbates (7 ). whereas a discrete molecular complex tural motif with potential fourfold symmetry,
We report the synthesis, structure, and [Mn(TMA-H2)2(H2O)4] is formed at RT (11). and the trimesic acid provides a threefold
some preliminary findings on the physical Our exploration of the solvothermal chemistry symmetry element. However, it is not the
and chemical properties of a highly porous of the copper trimesate system has resulted in direct combination of these two that creates
open-framework metal coordination poly- the discovery of HKUST-1 (12), in which the the cubic symmetry of the crystal, because
mer [Cu3(TMA)2(H2O)3]n (referred to as number of ancillary aqua ligands was reduced the Cu-Cu axis is not coincident with [100]
HKUST-1). This polymer forms face-cen- to just one per metal center. and has only a twofold crystallographic sym-
tered-cubic crystals that contain an inter- Single-crystal structure analysis (13) metry. Instead, the origin of the nanometer-
secting three-dimensional (3D) system of revealed that the polymer framework of sized channels can be considered as arising
large square-shaped pores (9 Å by 9 Å). HKUST-1 is composed of dimeric cupric tetra- from the formation of larger secondary build-
carboxylate units (Fig. 1), with a short Cu-Cu ing units (SBUs). The key SBU in HKUST-1
internuclear separation of 2.628(2) Å (number is an octahedral unit (Fig. 4) with Cu2 dimers
1
Department of Chemistry, Hong Kong University of
Science and Technology, Clear Water Bay, Kowloon,
in parentheses is the estimated standard devia- at its six vertices and four trimesate ions
Hong Kong, China. 2School of Chemistry, University tion of the final significant digit). The frame- tetrahedrally disposed as “panels” for four of
of Bristol, Cantock’s Close, Bristol BS8 1TS, UK. work is electrically neutral; the 12 carboxylate the eight triangular faces of the octahedron.
*To whom correspondence should be addressed. E- oxygens from the two TMA ligands bind to The framework was then achieved by con-
mail: chwill@ust.hk four coordination sites for each of the three necting the SBU with other units through

1148 19 FEBRUARY 1999 VOL 283 SCIENCE www.sciencemag.org

 REPORTS

Fig. 1 (left). Dicopper(II) tetracarboxylate building block for HKUST-1.

Key distances are Cu–Cu 5 2.628(2) Å, Cu–OCO 5 1.952(3) Å, and
Cu–OH2 5 2.165(8) Å. Fig. 2 (right). [Cu3( TMA)2(H2O)3]n polymer

Downloaded from http://science.sciencemag.org/ on March 20, 2018

framework viewed down the [100] direction, showing nanochannels with
fourfold symmetry.

corner sharing of the octahedra. The self-

assembly of these SBUs bears a strong re-
semblance to the formation of the molecular
“coordination aggregate” [{Pd(en)}6(tpt)4]
(where en is ethylenediamine and tpt is
tripyridyl-triazine) found by Fujita and co-
workers (17), which contains 10 molecular
fragments. Furthermore, such building blocks
were also found by Robson and coworkers
(18) in the cubic interpenetrated network
polymer [Cu3(tpt)4][ClO4]3. In this case, in-
dividual Cu atoms form the octahedron ver-
tices and create the corner sharing.
Many open zeolite structures also possess
large SBU fragments, such as double six-mem-
bered rings, or sodalite cages, which are then
connected to create large pore sizes. However, Fig. 4. Secondary building unit for
there are only a few zeolite structures, such as [Cu3( TMA)2(H2O)3]n, viewed along the [100]
Fig. 3. [Cu3( TMA)2(H2O)3]n viewed along the direction. The Cu2 dimers bridge to other such
faujasite, in which large pores intersect in a SBUs.
multidimensional sense, although Stucky and cell body diagonal [111], showing a hexagonal-
coworkers (1) recently synthesized a variety of shaped 18 Å window at the intersection of the
nanopores.
metal phosphates with three-dimensional inter- diffuse scattering model in its refinement.
secting 12-ring channels. In the case of Thermal gravimetric analysis (TGA) indicat-
HKUST-1, the relatively large SBU allows for Architectural modification should also be ed that there are up to 10 additional channel
similarly large-sized cavity formation. The possible with different polyfunctional car- water molecules per [Cu3(TMA)2(H2O)3]
structure is analogous to the [NaCl] rock-salt boxylates as network bridges. Recently, a 2D unit (21), a number that is also consistent
structure, with the octahedral building blocks network polymer [Zn{C6H4(COO)2}(H2O)]n with the packing of water molecules into
centered on one sublattice of sites and the wa- possessing a dizinc tetracarboxylate core was the accessible pore volume with the density
ter-filled cavities centered on the other. Al- formed by RT synthesis from dimethylform- of ice. This water capacity (28.3 weight %)
though the analogy to zeolite SBUs may be amide (DMF). It was proposed that this sub- is similar to that of Linde 133 molecular
useful in further assisting the design of other sequently formed a 3D network with 5 Å 1D sieves (16 ). Dehydration of the compound
open-framework coordination-based solids, one pore channels upon condensative loss of H2O can be achieved by heating to 100°C in air,
direct advantage of organic-based molecular (20). with a color change from turquoise to dark
building blocks is that facile pore-size engineer- In HKUST-1, the terminal axial water li- blue. Whereas the anhydrate is stable under
ing can be envisaged through the use of extend- gands are directed from the Cu atoms to the nitrogen, the sample rehydrates on expo-
ed ligands (19). Expanded ligands with en- interior of the nanopores. Because of disorder, sure to air.
forced trigonality, such as a carboxylate analog the additional water in the pore channels could The lability of the aqua ligands also allows
of tpt, thus offer the prospect of pore-size ex- not be directly located in the crystal structure their replacement by other groups. For exam-
pansion in the HKUST-1 system. analysis, but it was accounted for with a ple, treatment of the anhydrate [Cu3(TMA)2]n

www.sciencemag.org SCIENCE VOL 283 19 FEBRUARY 1999 1149

 REPORTS
with dry pyridine (py), followed by washing 10. S. O. H. Gutschke, A. M. Z. Slawin, P. T. Wood, Chem. presented at the 1st International Conference on
with dichloromethane, gave a quantitative yield Commun. 1996, 823 (1996). Inorganic Materials, Versailles, 16 to 19 September
11. Crystals of [Mn( TMA-H2)2(H2O)4 ] were formed by 1998].
of a green derivative [Cu3(TMA)2(py)3]n layer diffusion of ethanolic [TMA-H3 ] into aqueous 20. H. Li, M. Eddaoudi, T. L. Groy, O. M. Yaghi, J. Am.
z0.5pyz2H2O (22). Its x-ray diffraction pattern is Mn(OAc)2 at RT. The monoclinic crystal system data Chem. Soc. 120, 8571 (1998).
similar to that of HKUST-1 in d-spacing and are as follows: unit cell edges are a 5 5.178(2) Å, b 5 21. TGA results for HKUST-1 gave weight loss Dw 5
13.127(3) Å, and c 5 15.142(3) Å; interaxial angle b –28.2% from 25° to 120°C (–13 H2O), thermal sta-
line shape, demonstrating that chemical func- 5 97.74(2)°; and cell volume V 5 1019(1) Å3. bility from 120°C to 250°C, and Dw 5 –25.4% from
tionalization can be achieved without a loss of 12. In a typical synthesis, 1.8 mM of cupric nitrate 250° to 400°C (–CO2 and others). Further heating to
structural integrity. trihydrate was heated with 1.0 mM of trimesic acid 800°C resulted in a mixture of CuO and glassy C as
( TMA-H3) in 12 ml of 50:50 H2O:EtOH (EtOH, final products. TGA curves are available at www.
Although the resulting polymer [Cu3- ethyl alcohol) at 180°C for 12 hours in a Teflon- sciencemag.org/feature/data/986116.shl.
(TMA)2(py)3]n cannot be obtained by a direct lined 23-ml Parr pressure vessel. This gave tur- 22. The analytical and calculated (in parentheses) data
treatment of Cu(II) salts with TMA in pyridine quoise crystals up to dimensions of 80 mm in for [Cu3( TMA)2(py)3]z0.5(py)z2H2O are as follows: C,
solution (23), the use of either DMF or dimeth- ;60% yield along with Cu metal and Cu2O. Single- 43.54% (46.48%); H, 3.54% (3.01%); and N, 5.52%
crystal x-ray analysis of the turquoise crystals (5.30%). TGA showed Dw 5 –3.9% from 25° to
ylsulfoxide (DMSO) as the crystallizing solvent (HKUST-1) was carried out with a Siemens diffrac- 120°C and Dw 5 –54.2% from 120° to 400°C (–py,
affords phase-pure solids that are isostructural tometer that was equipped with a SMART charge- –CO2, and others).
with HKUST-1. These can be formed at RT in coupled device. 23. A 2D network polymer [Cu3( TMA)2(py)9]z3(py)z3H2O
13. Crystal data for HKUST-1 were measured as follows: (space group R-3c, a 5 19.142(5) Å, c 5 42.64(1) Å,
.80% yield and in multigram quantities. These C18H12O15Cu3, relative molecular mass Mr 5 658.9, and V 5 13,532 Å3) was formed with large 48-
solids still possess axial aqua ligands but con- cubic crystal system, space group Fm-3m, a 5 membered rings of six individual Cu atoms and six
tain channel DMF/DMSO and water (24). How 26.343(5) Å, V 5 18,280(7) Å3, formula units per cell TMA groups.
Z 5 16, density Dx 5 0.96 g cm–3, conventional 24. Analysis for the DMF product gave the best formu-
such polar organic solvents play a structure- discrepancy index R 5 5.99, and weighted wR2 5 lation as [Cu3( TMA)2(H2O)3]z2.5(DMF)z2.5(H2O), on
directing role in the formation of the tetracar- 16.78; for 43 least-squares parameters and 853 the basis of combined chemical and thermal gravi-
boxylate moieties remains to be established, reflections, diffraction angle 2Qmax 5 50°. The metric analyses. The analytical and calculated (in
structure was refined with SHELXL. A full descrip- parentheses) data are as follows: C, 34.6% (34.5%);
although changes in both solution speciation

Downloaded from http://science.sciencemag.org/ on March 20, 2018

tion of the x-ray analysis is available at www. H, 3.42% (3.89%); N, 4.01% (3.95%); Dw 5 –11.4%
and product solubilities are probably involved. sciencemag.org/feature/data/986116.shl. The co- from 25° to 120°C (H2O loss); and Dw 5 – 48.6%
Finally, the replacement of Cu by more ordinates are on deposit with the Cambridge Struc- from 150° to 400°C (DMF and CO2 loss). Variable-
oxophilic metals (Os2 and others) in the tural Database, deposit number 112954. temperature single-crystal studies of the DMSO de-
14. F. A. Cotton, Z. C. Mester, T. R. Webb, Acta Crystal- rivative showed no bound DMSO at RT; heating up to
framework of HKUST-1 should help achieve logr. B30, 2768 (1974); A. B. Brignole and F. A. 200°C produced intensity changes due to solvent loss
thermal stabilities in excess of 300°C. A Cotton, Inorg. Synth. 13, 81 (1972). (reflection 222 increases in intensity and reflection
TGA study of anhydrous [Er(TMA)] (25), 15. P. Ceccherini, M. Curini, M. C. Marcotullio, O. Rosati, 400 decreases). Cooling to RT resulted in a general
Tetrahedron 47, 7403 (1991). reversal of these trends.
which we have recently synthesized hydro-
16. D. W. Breck, Zeolite Molecular Sieves (Kreiger, Malabar, 25. Anhydrous [Er( TMA)] was synthesized hydrothermal-
thermally, shows no weight loss up to 500°C. FL, 1974), p. 48; ibid., p. 625. The BET data are available ly at 180°C in a manner similar to the synthesis of
Other metal substitutions may allow the in- at www.sciencemag.org/feature/data/986116.shl. HKUST-1; TGA under N2 produced Dw 5 , –1%
troduction of redox centers {Ru(II)-Ru(III)}, 17. M. Fujita et al., Angew. Chem. 37, 2082 (1998); M. from 25° to 500°C and Dw 5 – 45.7% from 500° to
Fujita and K. Ogura, Bull. Chem. Soc. Jpn. 69, 1471 650°C, corresponding to decarboxylation.
the incorporation of catalytic sites (Rh2), or a (1996). 26. We are grateful to the Research Grants Council of
switch from neutral to charged frameworks 18. B. F. Abrahams, S. R. Batten, H. Hamit, B. F. Hoskins, Hong Kong (RGC grants 6148-97P and 6061-98P)
{Re(III)-Re(III)}. R. Robson, Angew. Chem. Int. Ed. Engl. 35, 1690 and the Advanced Materials Research Institute
(1996). (AMRI-HKUST ) for financial support and to J. Zheng
19. Lattice expansion occurred in a family of Cu polymers and A. Siu for technical assistance.
containing N,N9 donor bridges [S. Katawa et al.,
References and Notes Inorg. Chem. 35, 4449 (1996); S. Kitagawa, paper 27 October 1998; accepted 4 January 1999
1. X. Bu, P. Feng, G. D. Stucky, Science 278, 2080 (1997).
2. M. E. Davis, Acc. Chem. Res. 26, 111 (1993); O. E.
Akporiaye, J. Chem. Soc. Chem. Commun. 1994,
1711 (1994); M. W. Anderson et al., Nature 367, 347
(1994); P. Feng, X. Bu, S. H. Tolbert, G. D. Stucky,
J. Am. Chem. Soc. 119, 24987 (1997).
Direct Evidence for R2 Rotons
3. S. T. Wilson, B. M. Lok, C. A. Messina, T. R. Cannon,
E. M. Flanigen, J. Am. Chem. Soc. 104, 1146 (1982); Having Antiparallel Momentum
P. Y. Feng, X. H. Bu, G. D. Stucky, Nature 388, 735
(1997).
4. B. F. Abrahams, B. F. Hoskins, D. M. Michail, R. Robson, and Velocity
Nature 369, 727 (1994); M. Fujita, Y. J. Kwon, S.
Washizu, K. Ogura, J. Am. Chem. Soc. 116, 1151 M. A. H. Tucker and A. F. G. Wyatt*
(1994).
5. O. M. Yaghi, G. Li, H. Li, Nature 378, 703 (1995);
O. M. Yaghi, C. E. Davis, G. Li, H. Li, J. Am. Chem. Soc. Experimental evidence is presented that shows that the momentum of a R2
119, 2861 (1997). roton (a particle-like excitation in liquid helium-4) is antiparallel to its velocity.
6. R. W. Gable, B. F. Hoskins, R. Robson, J. Chem. Soc. Although this is anticipated from the negative slope of the dispersion curve for
Chem. Commun. 1990, 1677 (1990); T. Soma, H.
Yuge, T. Iwamoto, Angew. Chem. Int. Ed. Engl. 33, these excitations, it has only been possible to test since the development of a
1665 (1994); L. Carlucci, G. Ciani, D. M. Proserpio, A. source of ballistic R2 rotons. The backward refraction of the quantum evap-
Sironi, J. Am. Chem. Soc. 117, 4562 (1995); G. B. oration process, which is the signature of antiparallel momentum and velocity,
Gardner, D. Venkataraman, J. S. Moore, S. Lee, Nature
374, 792 (1995); S. R. Batten, B. F. Hoskins, R. Robson,
is observed.
J. Am. Chem. Soc. 117, 5385 (1995); B. F. Abrahams,
S. R. Batten, H. Hamit, B. F. Hoskins, R. Robson, Chem. Particles in free space obey Newtonian laws equation of the form p 5 mv, and because
Commun. 1996, 1313 (1996); A. J. Blake et al., ibid. of motion at low speeds and relativistic laws mass (m) is always a positive quantity, p and
1997, 1005 (1997); A. J. Blake et al., ibid., p. 2027;
C. J. Kepert and M. J. Rosseinsky, ibid. 1998, 31, at high speeds. The momentum p and veloc- v are parallel. Particles that move in a medi-
(1998). ity v of such a particle are connected by an um do not necessarily have p parallel to v
7. S. Subramanian and M. Zaworotko, Angew. Chem. Int. because the momentum is a composite quan-
Ed. Engl. 34, 2127 (1995).
School of Physics, University of Exeter, Stocker Road, tity involving both the particle and the reac-
8. R. Pech and J. Pickardt, Acta Crystallogr. C44, 992
Exeter EX4 4QL, UK. tion of the medium to its motion. Liquid 4He
(1988).
9. S. S.-Y. Chui and I. D. Williams, ibid. C55, 194 (1999). *To whom correspondence should be addressed. at temperatures T , 2.1 K has particle-like

1150 19 FEBRUARY 1999 VOL 283 SCIENCE www.sciencemag.org

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
Stephen S.-Y. Chui, Samuel M.-F. Lo, Jonathan P. H. Charmant, A. Guy Orpen and Ian D. Williams

Science 283 (5405), 1148-1150.

DOI: 10.1126/science.283.5405.1148

Downloaded from http://science.sciencemag.org/ on March 20, 2018

ARTICLE TOOLS http://science.sciencemag.org/content/283/5405/1148

REFERENCES This article cites 28 articles, 1 of which you can access for free
http://science.sciencemag.org/content/283/5405/1148#BIBL

PERMISSIONS http://www.sciencemag.org/help/reprints-and-permissions

Use of this article is subject to the Terms of Service

Science (print ISSN 0036-8075; online ISSN 1095-9203) is published by the American Association for the Advancement of
Science, 1200 New York Avenue NW, Washington, DC 20005. 2017 © The Authors, some rights reserved; exclusive licensee
American Association for the Advancement of Science. No claim to original U.S. Government Works. The title Science is a
registered trademark of AAAS.