Abstract
The First-principles Bottom-up (FPBU) procedure is applied to rationalize the different macroscopic magnetic properties of two compounds that were expected to be isostructural: bis(2-bromo-3-methylpyridine)dibromocopper( II), 1, whose crystals present dominant ferromagnetic interactions, and bis(2-chloro-3-methylpyridine)dichlorocopper( II), 2, that shows dominant antiferromagnetic behavior. Our FPBU analysis concludes that 1 presents a dominant ferromagnetic interaction of 1.16 cm-1 and other two nonnegligible smaller interactions of opposite sign (-0.11 and 0.13 cm-1). Contrarily, the dominant radical-pair interaction in 2 is antiferromagnetic (-2.37 cm-1), in addition to three other non-negligible smaller magnetic couplings (0.48, -0.29, and -0.20 cm-1). In 1, these magnetic interactions generate a 2D magnetic topology of isolated planes, each made of weakly interacting parallel ferromagnetic chains, while in 2 they generate a 2D magnetic topology that can be described as isolated parallel double-decker planes, each of them made by weakly connected antiferromagnetic dimers. The computed magnetic susceptibility curve that results after applying the FPBU procedure fullymatches the experimental one in both systems. Furthermore, since in both systems, the weaker magnetic interactions are one order of magnitude smaller than the dominant coupling, the magnetic susceptibility curve does not vary significantly whether including all interactions or only the dominant ones. Thus, the FPBU analysis quantitatively traces down the origin of the different magnetic behavior of 1 and 2 as due to the change in sign of their dominant magnetic interactions. We have been able to connect such a change in nature of the dominant magnetic interaction with a change in the conformation of the ligands, which converts from anti in bis(2-bromo-3-methylpyridine) (1) to syn in bis(2-chloro-3-methylpyridine) (2), confirming the previous hypothesis.
Published as part of the special collection of articles derived from the 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012).
Electronic supplementary material The online version of this article (doi:10.1007/s00214-013-1331-2) contains supplementary material, which is available to authorized users.
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Johnston DC, Johnson JW, Goshorn DP, Jacobson AJ (1987) Phys Rev B Condens Matter Mater Phys 35(1):219
Barnes T, Riera J (1994) Phys Rev B Condens Matter Mater Phys 50(10):6817
Eccleston RS, Barnes T, Brody J, Johnson JW (1994) Phys Rev Lett 73(19):2626
Schwenk H, Konig D, Sieling M, Schmidt S, Palme W, Luthi B, Zvyagin S, Eccleston RS, Azuma M, Takano M (1997) Physica B 237–238:115
Eccleston RS, Mutka H, Payen C (1997) Physica B 234–236:895
Garrett AW, Nagler SE, Barnes T, Sales BC (1997) Phys Rev B Condens Matter 55(6):3631
Garrett AW, Nagler SE, Tennant DA, Sales BC, Barnes T (1997) Phys Rev Lett 79(4):745
Herringer SN, Turnbull MM, Landee CP, Wikaira JL (2011) Dalton Trans 40:4242
Deumal M, Bearpark MJ, Novoa JJ, Robb MA (2002) J Phys Chem A 106:1299
Szabo A, Ostlund NS (1989) Modern quantum chemistry: introduction to advanced electronic structure theory. McGraw-Hill Inc., New York
Hohenberg P, Kohn W (1964) Phys Rev 136:B864
Clarke CS, Jornet-Somoza J, Mota F, Novoa JJ, Deumal M (2010) J Am Chem Soc 132:17817
Deumal M, Giorgi G, Robb MA, Turnbull MM, Landee CP, Novoa JJ (2005) Eur J Inorg Chem 23:4697
Vela S, Deumal M, Turnbull MM, Novoa JJ (2012) Polyhedron. doi:10.1016/j.poly.2012.07.085
Jornet J, Li L, Turnbull MM, Landee CP, Deumal M, Novoa JJ, Wikaira JL (2007) Inorg Chem 46:11254
Novoa JJ, Deumal M, Jornet-Somoza J (2011) Chem Soc Rev 40:3182–3212
Noodleman L (1981) J Chem Phys 74:5737
Noodleman L, Davidson ER (1986) Chem Phys 109:131
Jornet-Somoza J, Deumal M, Turnbull MM, Novoa JJ (2009) Polyhedron 28:1965
Parr EG, Yang W (1989) Density functional theory of atoms and molecules. Oxford University Press, New York
Becke AD (1988) Phys Rev A 38:3098
Becke AD (1993) J Chem Phys 98:5648
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785
Schafer A, Horn H, Ahlrichs R (1992) J Chem Phys 97:2751
Ditchfield R, Hehre WJ, Pople JA (1971) J Chem Phys 54:724
Frisch MJ et al (2009) Gaussian 09, Revision B.1. Gaussian, Inc, Wallingford
Shortsleeves KC, Dawe LN, Landee CP, Turnbull MM (2009) Inorg Chim Acta 362:1859
Awwadi F, Willett RD, Twamley B (2011) Cryst Growth Des 11:5316
van Albada GA, Tanase S, Mutikainen I, Turpeinen U, Reedijk J (2008) Inorg Chim Acta 361:1463
Awwadi FF, Willett RD, Haddad SF, Twamley B (2006) Cryst Growth Des 6:1833
Espallargas GM, van de Streek J, Fernandes P, Florence AJ, Brunelli M, Shankland K, Brammer L (2010) Angew Chem Int Ed 49:8892
Lah N, Leban I (2010) Struct Chem 21:263
Singh P, Jeter DY, Hatfield WE, Hodgson DJ (1972) Inorg Chem 11:1657
Duckworth VF, Stephenson NC (1969) Acta Crystallogr Sect B Struct Crystallogr Cryst Chem 25:2245
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Vela, S., Deumal, M., Turnbull, M.M., Novoa, J.J. (2014). A theoretical analysis of the magnetic properties of the low-dimensional copper(II)X2(2-X-3-methylpyridine)2 (X = Cl and Br) complexes. In: Novoa, J., Ruiz López, M. (eds) 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012). Highlights in Theoretical Chemistry, vol 5. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41272-1_25
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DOI: https://doi.org/10.1007/978-3-642-41272-1_25
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