1
56
S. Giri et al. / Inorganica Chimica Acta 368 (2011) 152–156
Scheme 3.
equation 3 and 4. In this case all the exchange interactions (J’s) are
crystallographic equivalent and it is less important to calculate all
the energy states.
available in the supporting documents. CCDC 796253 contains
the supplementary crystallographic data for complex 1. These data
E
LS1 ꢀ EHS ¼ J þ J
ð3Þ
1
2
E
LS2 ꢀ EHS ¼ 2J1
ð4Þ
The spin flip DFT approach is often used to estimate the ex-
References
change coupling for polynuclear complexes [15]. In the present
work we used this approach to calculate the broken symmetry
states as implemented in the ORCA program package [16]. The sin-
gle point energy calculations were carried out with the geometry
built from experimental atomic coordinates. We have used the
B3LYP hybrid density functional [17] and the TZVP basis set for
all atoms [18]. We also have taken advantage of the RI approxima-
tion with auxiliary TZV/J coulomb fitting basis sets to accelerate the
calculations [19]. All energy calculations were performed including
a tight SCF convergence criteria (Grid4). Exchange coupling con-
[
1] (a) O. Kahn, Molecular Magnetism, VCH Publishers, New York, 1993.;
b) E.I. Solomon, U.M. Sundram, T.E. Machonkin, Chem. Rev. 96 (1996) 2563;
(
(c) B. Chen, M.E. Eddaoudi, T.M. Reineke, J.W. Kampf, M. O’Keette, O.M. Yaghi, J.
Am. Chem. Soc. 122 (2000) 11559;
(
(
d) J.S. Miller, A.J. Epstein, Angew. Chem., Int. Ed. Engl. 33 (1994) 385;
e) J. Mukherjee, R. Mukherjee, Inorg. Chim. Acta 337 (2002) 429.
[2] (a) S. Koner, S. Saha, T. Mallah, K. Okamoto, Inorg. Chem. 43 (2004) 840;
(b) S. Mukherjee, B. Gole, R. Chakrabarty, P.S. Mukherjee, Inorg. Chem. 48
(
(
2009) 11325;
c) T.C. Stamatatos, G.S. Papaefstathiou, L.R. MacGillivray, A. Escuer, R. Vicente,
E. Ruiz, S.P. Perlepes, Inorg. Chem. 46 (2007) 8843.
stant (J
i
) can be obtained using of the Ising approach in which bro-
[3] (a) C. Diedrich, R.J. Deeth, Inorg. Chem. 47 (2008) 2494;
(
(
b) E. Ruiz, P. Alemany, S. Alvarez, J. Cano, J. Am. Chem. Soc. 119 (1997) 1297;
c) E. Ruiz, P. Alemany, S. Alvarez, J. Cano, Inorg. Chem. 36 (1997) 3683.
ken symmetry states were directly considered as eigenstates of the
corresponding Hamiltonian [20].
[
4] (a) J. Fielden, J. Sprott, D. Long, P. Ko1gerler, L. Cronin, Inorg. Chem. 45 (2006)
886;
b) A. Burkhardt, E.T. Spielberg, H. Görls, W. Plass, Inorg. Chem. 47 (2008)
485;
c) S. Wang, S.J. Trepanier, J.C. Zheng, Z. Pang, M.J. Wagner, Inorg. Chem. 31
(1992) 2118;
d) C.P. Poole Jr., T. Datta, H.A. Farach, Copper Oxide Superconductors, John
Wiley and Sons, New York, 1988.;
e) C.N. Rao, A.K. Ganguli, Chem. Soc. Rev. 24 (1995) 1.
[5] G. Kolks, S.J. Lippard, J.V. Wszczak, H.R. Lilienthalle, J. Am. Chem. Soc. 104
1982) 717.
2
(
2
(
4
. Conclusions
A nearly planer tetranuclear Cu(II) complex with 2-(pyridine-2-
(
yliminomethyl)-phenol have been synthesized and structurally
characterized by X-ray crystallography. Structural analysis reveals
that the equivalent copper ions are penta-coordinated with a
square pyramidal geometry. Di-phenoxo and NCN bridging groups
alternatively link the copper ions to form a distorted rectangular
structure. Magneto-structural studies show the coexistence of
strong and moderate antiferromagnetic interactions between the
copper centers. Values of exchange coupling parameters estimated
from DFT calculations agree well with those extracted from the
theoretically fitted susceptibility data.
(
(
[
6] V. Tangoulis, C.P. Raptopoulou, S. Paschalidou, A.E. Tsohos, E.G. Bakalbassis, A.
Terzis, S.P. Perlepes, Inorg. Chem. 36 (1997) 5270.
[7] J. Drummond, J.S. Wood, J. Chem. Soc., Dalton Trans. (1972) 365.
[
[
8] W.E. Hatfield, F.L. Bunger, Inorg. Chem. 8 (1969) 1194.
9] CRYSALIS, Oxford Diffraction Ltd., Abingdon, UK, 2006
[
10] G.M. Sheldrick, SHELXS97 and SHELXL97, Programs for Crystallographic Solution
and Refinement, Acta Crystallogr., Sect. A 64 (2008) 112.
11] ABSPACK, Oxford Diffraction Ltd., Oxford, UK, 2005
12] R.W. Jotham, S.F.A. Kettle, Inorg. Chim. Acta 4 (1970) 145.
13] D. Venegas-Yazigi, D. Aravena, E. Spodine, E. Ruizand, S. Alvarez, Coord. Chem.
Rev. 254 (2010) 2086.
[
[
[
Acknowledgments
[
[
14] L. Gutiérrez, G. Alzuet, J. Borrás, A. Castiñeiras, A. Rodríguez-Fortea, E. Ruiz,
Inorg. Chem. 40 (2001) 3089.
15] (a) A. Ozarowski, I.B. Szyma n´ ska, T. Muziol, J. Jezierska, J. Am. Chem. Soc. 131
(2009) 10279;
S. Giri and S. Biswas acknowledge Council of Scientific and
Industrial Research (Grant No. 09/080 (0639)/2009-EMR-I and
0
9/028 (0732)/2008-EMR-I) New Delhi, India for awarding fellow-
(b) C. Baffert, M. Orio, D.A. Pantazis, C. Duboc, A.G. Blackman, G. Blondin, F.
Neese, A. Deronzier, M. Collomb, Inorg. Chem. 48 (2009) 10281;
ship. MGBD acknowledges EPSRC and the University of Reading for
funding the X-Calibur system. SKS acknowledges DST Unit on
Nanoscience and Centre for Nanotechnology for supporting infra-
structural facilities.
(
4
c) G.H. Spikes, S. Sproules, E. Bill, T. Weyhermüller, K. Wieghardt, Inorg. Chem.
7 (2008) 10935;
(d) L. Noodleman, E.J. Baerends, J. Am. Chem. Soc. 106 (1984) 2316.
16] F. Neese, ORCA, An ab initio, Density Functional and Semiempirical Program
Package, Version 2.7, Universität Bonn, Bonn, Germany, 2009.
17] (a) A.D. Becke, J. Chem. Phys. 98 (1993) 5648;
[
[
(
(
b) C.T. Lee, W.T. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785;
c) A.D. Becke, Phys. Rev. A 38 (1988) 3098.
Appendix A. Supplementary material
[
18] A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 100 (1994) 5829.
Extended hydrogen bonding network (space filling model) and
Mulliken atomic spin populations of different spin states are
[19] F. Weigend, Phys. Chem. Chem. Phys. 8 (2006) 1057.
[20] P. Albores, E. Rentschler, Inorg. Chem. 49 (2010) 8953.