RSC Advances
Communication
structure via one unexpected oxalate anion. The terminal 10 J. C. Tan and A. K. Cheetham, Chem. Soc. Rev., 2011, 40,
chlorine atoms act as bridges between the monomeric units in 1059–1080.
this coordination polymer. As far as we know, this is the rst 11 W. Li, M. S. R. N. Kiran, J. L. Manson, J. A. Schlueter,
time that the [CuClO N ] and [N –Cu–Ox–Cu–N ] coordina-
A. Thirumurugan, U. Ramamurty and A. K. Cheetham,
3
pz
pz
pz
tion environments are reported. In the supramolecular network
Chem. Commun., 2013, 49, 4471–4473.
an interesting 2D structure with layered architecture formed 12 S. Varughese, M. S. R. N. Kiran, U. Ramamurty and
from polymeric chains interconnected by Cu2–Cl1–Cu1 bridges G. R. Desiraju, Angew. Chem., Int. Ed., 2013, 52, 2701–2712.
is formed along the b-axis. Additionally, the values of hardness, 13 J. C. Tan, J. D. Furman and A. K. Cheetham, J. Am. Chem.
Young’s modulus, and elastic recovery of this structure have Soc., 2009, 131, 14252–14254.
been determined by means of nanoindentation. The mechan- 14 S. S. Han and W. A. Goddard, J. Phys. Chem. C, 2007, 111,
ical characterization of this kind of hybrid material is an 15185–15191.
important asset to crystal engineering since durability and 15 W. L. Driessen, Recl. Trav. Chim. Pays-Bas, 1982, 101, 441–
reliability, which are dictated by the mechanical properties, are 443.
important factors for their potential applications in sensors, 16 W. C. Oliver and G. M. Pharr, J. Mater. Res., 1992, 7, 1564–
catalysts and gas storage, among others.
1583.
1
1
7 A. Fischer-Cripps, Nanoindentation, Springer, New York,
USA, 2004.
8 E. Pellicer, A. Varea, S. Pan ´e , B. J. Nelson, E. Men ´e ndez,
M. Estrader, S. Suri n˜ ach, M. D. Bar ´o , J. Nogu ´e s and J. Sort,
Adv. Funct. Mater., 2010, 20, 983–991.
Acknowledgements
The nancial support from the MAT2011-27380-C02-01 and the
MAT2011-27225 research projects from the Spanish MINECO,
8 8 2 4 3
and the 2014-SGR-1015 and the 2014-SGR-260 projects from the 19 Analysis for C H ClCu N O calcd/found (%): C, 25.92/25.72;
Generalitat de Catalunya are acknowledged. M. D. B. was
partially supported by an ICREA-Academia award. A. L_M.
thanks the FI-2010 scholarship given by the Government of
Catalonia. M. G. acknowledges the support of the Secretary for
Universities and Research of the Government of Catalonia and
the COFUND Programme of the Marie Curie Actions of the 7th R
H, 2.17/2.13, N, 15.11/15.04, Cu, 34.28/33.96, giving
satisfactory C, H, N and Cu elemental analyses. IR (KBr,
cm ): 3190, 3120 n(C–H)ar; 2940, 2920 n(C–H)al; 1650
[n(C]C), n(C]N)]ar; 1400 [d(C]C), d(C]N)]ar and 773 g(]
C–H)oop present shis (in relation with the free ligand)
produced by the coordination with copper(II); moreover,
ꢀ
1
&
‘
D Framework Programme of the European Union for the
Beatriu de Pinos’ contract (2013 BP-B 00077). E. P. acknowl-
edges the Spanish MINECO for the ‘Ramon y Cajal’ contract
RYC-2012-10839).
the bands at 472, 428 n(Cu–N); 550, n(Cu–O); 600 g (Cu–O)
as
and 356, 322 n(Cu–Cl) also corroborate the copper
ꢀ
3
coordination. Conductivity (1.02 ꢁ 10 M in methanol):
ꢀ
1
2
ꢀ1
(
32 U
cm mol , in agreement with a non-electrolyte
ꢀ
3
complex; UV-vis (1.1 ꢁ 10
M in methanol) exhibits a
single band at 620 nm.
References
2
0 G. Mezei, M. Rivera-Carrillo and R. G. Raptis, Inorg. Chim.
1
2
3
T. R. Cook, Y.-R. Zheng and P. J. Stang, Chem. Rev., 2013, 113,
34–777.
M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter,
M. O’Keeffe and O. M. Yaghi, Science, 2002, 295, 469–472.
I.-H. Park, A. Chanthapally, Z. Zhang, S. S. Lee,
Acta, 2004, 357, 3721–3732.
21 G. Mezei, R. G. Raptis and J. Telser, Inorg. Chem., 2006, 45,
8841–8843.
22 M. Rivera-Carrillo, I. Chakraborty, G. Mezei, R. D. Webster
and R. G. Raptis, Inorg. Chem., 2008, 47, 7644–7650.
7
M. J. Zaworotko and J. J. Vittal, Angew. Chem., Int. Ed., 23 P. A. Angaridis, P. Baran, R. Boca, F. Cervantes-Lee,
2
014, 53, 414–419.
W. Haase, G. Mezei, R. G. Raptis and R. Werner, Inorg.
Chem., 2002, 41, 2219–2228.
4
5
6
7
S. Xiang, Y. He, Z. Zhang, H. Wu, W. Zhou, R. Krishna and
B. Chen, Nat. Commun, 2012, 3, 954–963.
X.-L. Yang, M.-H. Xie, C. Zou, Y. He, B. Chen, M. O’Keeffe and
C.-D. Wu, J. Am. Chem. Soc., 2012, 134, 10638–10645.
Y. Zhao, D.-S. Deng, L.-F. Ma, B.-M. Ji and L.-Y. Wang, Chem.
Commun., 2013, 49, 10299–10301.
24 M. F. Castello, C. V. Grupioni, R. S. Nunes and J. M. Luiz, J.
Therm. Anal. Calorim., 2014, 117, 1145–1150.
25 X.-D. Zhang, Z. Zhao, J.-Y. Sun, Y.-Ch. Ma and M.-L. Zhu, Acta
Crystallogr., Sect. E: Struct. Rep. Online, 2005, 61, m2643–
m2645.
L. Croitor, E. B. Coropceanu, D. Chisca, S. G. Baca, J. van 26 H.-D. Wang, Y.-L. Zhou, H.-Y. He, X.-H. Tu and L.-G. Zhu,
Leusen, P. K ¨o gerler, P. Bourosh, V. C. Kravtsov, D. Grabco,
C. Pyrtsac and M. S. Fonari, Cryst. Growth Des., 2014, 14,
Acta Crystallogr., Sect. E: Struct. Rep. Online, 2006, 62,
m1081–m1082.
3
015–3025.
27 Traces of oxalic acid were determined by
spectrophotometric method under aerobic conditions aer
stirring a basic solution of CuCl in ethanol. The oxalic
acid concentration was determined from the decrease in
a
8
9
L. J. McCormick, S. G. Duyker, A. W. Thornton, C. S. Hawes,
M. R. Hill, V. K. Peterson, S. R. Batten and D. R. Turner,
Chem. Mater., 2014, 26, 4640–4646.
F. Gul-E-Noor, M. Mendt, D. Michel, A. P ¨o ppl,
H. Krautscheid, J. Haase and M. Bertmer, J. Phys. Chem. C,
2
2
+
absorbance of the Cu band and the increase of the Cu–
Ox one, changing the colour from blue to yellow.
2013, 117, 7703–7712.
32374 | RSC Adv., 2015, 5, 32369–32375
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