Z = 4, Dc = 1.488 g cm23, T = 298(2) K, crystal size 0.40 6 0.15 6
0.10 mm3, R = 0.0783, Rw = 0.1851, GOF = 0.670 with I . 2.00s(I).
CCDC 633740.
of the nanoclusters are possibly related to the self-assembly of the
tubular architectures under suitable conditions.
Crystal data for 3: [NiII52yZnIIy(OC16H11N4)6]Cl4?5H2O (y = 3),
All the previous characterizations have confirmed that single-
crystal metal–organic microtubular architectures have been
successfully fabricated from designed D3 symmetrical nanoclusters,
so how do they form? Qian and co-workers reported tellurium
nanotubes formed under hydrothermal conditions, giving us some
enlightenment.10 The groove-like prisms and cones with one end
closed (Fig. 1) indicates they possibly share similar mechanism of
formation as the tellurium nanotubes. Namely, under our
experimental conditions, the first step is possibly that the clusters
form some nanoparticles, and then because ligand 1 is formed
in situ and needs to react with metal ions to form the clusters, the
speed of the formation of the clusters will be slow and can not
provide enough clusters for the growth of the growing rodlike
crystals, leading to undersaturation in the central part of the
growing regions of crystal nanoparticles. The continuous feeding
of clusters on the surface of nanoparticles can diffuse into two
directions: circumferential diffusion and diffusion parallel to the
tuber axis, resulting in formation of groove-like and tubular
architectures. The details of the mechanism is still underway.
In summary, we have, for the first time, synthesized crystal
microtubes consisting of D3 symmetrical nanoclusters with a
capped triple-helix pentanuclear M5O6 core by facile and reliable
hydrothermal treatments. Although the exact mechanism of the
formation of these microtubes is still unclear, it does demonstrate
that nanoclusters with desired symmetry can be rationally designed
and these metal–organic clusters can be assembled into tubular
architectures under appropriate conditions. Their D3 symmetrical
characteristics in the structures and the formation speed of the
clusters possibly play an important role in the formation of the
tubular architectures. Therefore, preparation of tubular architec-
tures of various dimensions from some highly symmetrical metal–
organic coordination complexes is thus promising and may
facilitate the research and application of tubular structures in a
much wider range.
monoclinic, space group P21/c, a = 13.0667(8), b = 26.6002(17), c =
3
˚
˚
29.0855(18) A, b = 104.976(3)u, V = 9766.1(11) A , Z = 4, Dc
=
1.482 g cm23, T = 298(2) K, crystal size 0.20 6 0.19 6 0.10 mm3,
R = 0.0888, Rw = 0.2209, GOF = 0.929 with I . 2.00s(I). CCDC 633739.
Crystal data for 4: [NiII5(OC16H11N4)6]Cl4?4H2O, monoclinic, space
˚
group P21/c, a = 13.1351(11), b = 26.668(2), c = 29.0984(19) A, b =
105.009(3)u, V = 9845.1(13) A , Z = 4, Dc = 1.457 g cm23, T = 298(2) K,
3
˚
crystal size 0.20 6 0.08 6 0.08 mm3, R = 0.0518, Rw = 0.1996, GOF =
1.042 with I . 2.00s(I). CCDC 633741.
For crystallographic data in CIF or other electronic format see DOI:
10.1039/b711695k
1 S. Iijima, Nature, 1991, 354, 56.
2 Y. Wang, T. Herricks and Y. Xia, Nano Lett., 2003, 3, 1163; P. X. Gao,
Y. Ding and Z. L. Wang, Nano Lett., 2003, 3, 1315; L. Guo, Y. L. Ji,
H. B. Xu, P. Simon and Z. Y. Wu, J. Am. Chem. Soc., 2002, 124, 14864;
C. Saridara, R. Brukh, Z. Iqbal and S. Mitra, Anal. Chem., 2005, 77,
ˇ
1183; J. Munoz, M. Gallego and M. el Valca´rcel, Anal. Chem., 2005, 77,
5389; L. Qian, F. Teng, Z.-S. Jin, Z.-J. Zhang, T. Zhang, Y.-B. Hou,
S.-Y. Yang and X.-R. Xu, J. Phys. Chem. B, 2004, 108, 13928; H.-S.
Kim, H. Lee, K.-S. Han, J.-H. Kim, M.-S. Song, M.-S. Park, J.-Y. Lee
and J.-K. Kang, J. Phys. Chem. B, 2005, 109, 8983; Z. Zhao, I. A.
Banerjee and H. Matsui, J. Am. Chem. Soc., 2005, 127, 8930; N. Wong,
S. Kam, Z. Liu and H. Dai, Angew. Chem., Int. Ed., 2006, 45, 577.
3 M. M. Reches and E. Gazit, Science, 2003, 300, 625; M. Masuda and
T. Shimizu, Langmuir, 2004, 20, 5969; S. Kamiya, H. Minamikawa,
J. H. Jung, B. Yang, M. Masuda and T. Shimizu, Langmuir, 2005, 21,
743; L. Zhi, T. Gorelik, J. Wu, U. Kolb and K. Mu¨llen, J. Am. Chem.
Soc., 2005, 127, 12792; J. Du, L. Fu, Z. Liu, B. Han, Z. Li, Y. Liu,
Z. Sun and D. Zhu, J. Phys. Chem. B, 2005, 109, 12772; T. Saito,
S. Ohshima, W.-C. Xu, H. Ago, M. Yumura and S. Iijima, J. Phys.
Chem. B, 2005, 109, 10647; H. Yu, Z. Zhang, M. Han, X. Hao and
F. Zhu, J. Am. Chem. Soc., 2005, 127, 2378; Y. Wang and K. Wu,
J. Am. Chem. Soc., 2005, 127, 9686; Y. Zhao, X. Cao and L. Jiang,
J. Am. Chem. Soc., 2007, 129, 764; H. Y. Lee, S. R. Nam and J.-I. Hong,
J. Am. Chem. Soc., 2007, 129, 1040.
4 C.-Y. Su, A. M. Goforth, M. D. Smith, P. J. Pellechia and H.-C.
Zr Loye, J. Am. Chem. Soc., 2005, 126, 3576.
5 O.-S. Jung, Y. J. Kim, Y.-A. Lee, J. K. Park and H. K. Chae, J. Am.
Chem. Soc., 2000, 122, 9921; M. Eddaoudi, D. B. Moler, H. L. Li,
B. L. Chen, T. M. Reineke, M. O’Keeffe and O. M. Yaghi, Acc. Chem.
Res., 2001, 34, 319; M. Eddaoudi, J. Kim, N. Rosi, D. Vodak,
J. Wachter, M. O’Keefe and O. M. Yaghi, Science, 2002, 295, 469;
N. L. Rosi, J. Eckert, M. Eddaoudi, D. Vodak, J. Kim, M. O’Keefe and
O. M. Yaghi, Science, 2003, 300, 1127; G. Ferey, C. Mellot-Draznieks,
C. Serre, F. Millange, J. Dutour, S. Surble and I. Margiolaki, Science,
2005, 309, 2040; B. Xiao, P. S. Wheatley, X. Zhao, A. J. Fletcher, S. Fox,
A. G. Rossi, L. L. Megson, S. Bordiga, L. Regli, K. Mark Thomas and
R. E. Morris, J. Am. Chem. Soc., 2007, 129, 1203; C.-I. Yang,
W. Wernsdorfer, G.-H. Lee and H.-L. Tsai, J. Am. Chem. Soc., 2007,
129, 456; C. J. Milios, A. Vinslava, P. A. Wood, S. Parsons,
W. Wernsdorfer, G. Christou, S. P. Perlepes and E. K. Brechin,
J. Am. Chem. Soc., 2007, 129, 8.
This work is supported financially by the National Natural
Science Foundation of China (grant No. 20471033), the Province
Natural Science Foundation of Shanxi Province of China (grant
No. 20051013) and the Overseas Returned Scholar Foundation of
Shanxi Province of China in 2006.
Notes and references
{ Elemental analysis (EA) and ICP for 2: calc. for C96H74Cl4Cu1.43N24-
Ni4.57O10.5: C 51.64; H 3.34; N 15.06; Ni 12.01; Cu 4.07. Found: C 51.32; H
3.35; N 14.82; Ni 12.04; Cu 4.08%. IR (KBr) n/cm21: 1612s, 1541m, 1452m,
1398m, 1339s, 1285m, 1066m, 876w, 746s.
The synthesis of complex 3 was by the same procedure as for complex 2
with replacement of CuO by ZnO. Yellow tubular crystals were collected in
30% yield. EA and ICP: calc. for C96H74Cl4N24Ni2Zn3O10: C 52.91; H 3.42;
N 15.43; Ni 5.39; Zn 9.00. Found: C 52.53; H 3.45; N 15.28%. ICP: Ni
5.74; Zn 8.96%. IR (KBr) n/cm21: 1611s, 1542m, 1455m, 1399m, 1340s,
1284m, 1066m, 874w, 743s.
6 X. Sun, D. W. Johnson, K. N. Raymond and E. H. Wong, Inorg.
Chem., 2001, 40, 4448; X. Sun, D. W. Johnson, K. N. Raymond and
E. H. Wong, J. Am. Chem. Soc., 2001, 123, 2752; X. Sun,
D. W. Johnson, D. L. Caulder, R. E. Powers, K. N. Raymond and
E. H. Wong, Angew. Chem., Int. Ed., 1999, 38, 1303.
7 M. H. W. Lam, S. T. C. Cheung, K.-M. Fung and W.-T. Wong, Inorg.
Chem., 1997, 36, 4618.
8 S. L. Heath, R. H. Laye, C. A. Muryn, N. Lima, R. Sessoli, R. Shaw,
S. J. Teat, G. A. Timco and R. E. P. Winpenny, Angew. Chem., Int. Ed.,
2004, 43, 6132; F. K. Larsen, E. J. L. McInnes, H. E. Mkami,
J. Overgaard, S. Piligkos, G. Rajaraman, E. Rentschler, A. A. Smith,
G. M. Smith, V. Boote, M. Jennings, G. A. Timco and R. E. P.
Winpenny, Angew. Chem., Int. Ed., 2003, 42, 101.
The synthesis of complex 4 was by the same procedure as for complex 2
but without any CuO. Red brown tubular crystals were collected in 15%
yield. EA and ICP: calc. for C96H74Cl4N24Ni5O10: C 53.40; H 3.45; N
15.57; Ni 13.59. Found: C 52.92; H 3.50; N 15.42. Ni 13.40%. IR (KBr)
n/cm21: 1612s, 1543m, 1454m, 1399m, 1339s, 1284m, 1067w, 997m, 876w,
746s.
9 S. Leclair, P. Baillargeon, R. Skouta, D. Gauthier, Y. Zhao and
Y. L. Dory, Angew. Chem., Int. Ed., 2004, 43, 349; R. Harada,
§ Crystal data for 2: [NiII52xCuIIx(OC16H11N4)5(OC16H10N4)-
Y. Matsuda, H. Okawa and Takahiko Kojima, Angew. Chem., Int. Ed.,
2004, 43, 1825.
10 G. Xi, Y. Peng, W. Yu and Y. Qian, Cryst. Growth Des., 2005, 5, 325.
¯
CuI(H2O)]Cl4?3.5H2O (x = 0.43), monoclinic, space group P21/c, a =
3
˚
˚
13.259(5), b = 26.875(10), c = 28.993(9) A, b = 105.48(1)u, V = 9956(6) A ,
This journal is ß The Royal Society of Chemistry 2007
Chem. Commun., 2007, 4785–4787 | 4787