“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

W. M. Reiffa, M. Feistb, and E. Kemnitzb

aDepartment of Chemistry, Northeastern University, Boston MA, 02115, USA; E-mail:w.reiff@neu.edu; bInstitut für Chemie der Humboldt Universität,

Brook-Taylor-Str. 2, D-12489 Berlin, Germany, e-mail: feistm@chemie.hu-berlin.de, erhard.kemnitz@chemie.hu-berlin.de

Exotic Dimers Part Two: A High-Spin Ferrous Dimer that

Exhibits Genuine Spontaneous Long Range 3D-

Magnetic Order in Zero Field and Metamagnetism

“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

Simple dimers with antiferromagnetic intradimer exchange are generally not expected to exhibit spontaneous, long range antiferromagnetic order in zero field owing to their non-magnetic, singlet (STotal = o) ground state. However, some exceptions exist. Thus in the series Cs3Cr2X9 (X = Cl, Br, I); the chloride and bromide magnetically order but only in very large externally applied fields, pulsed fields out to ~ 42 T for T ~ 0.5 K (so called field induced magnetic ordering(1)). The iodide does indeed order in zero field at ~7 K as confirmed via inelastic neutron scattering(2).

(1)Ajiro, Y; Inagaki, T; Asano, H; Mitamura, H; and Goto, T, J. Magn. Magnet. Mat., 2003, 272-276, 218 219.(2)Leuenberger, B., Güdel, H. and Fischer, P., Phys. Rev. Lett. 1985,55, 2983

The possible interdimer magnetic exchange interactions in such dimers are weak and correspond primarily to close contacts of delocalized metal electron spin density on the halogens as opposed to direct interdimer metal-metal magnetic exchange interactions. Hence, the zero field ordering of the above iodide is not surprising and is fully consistent with its well established largest polarizability in the halogen series. This in turn leads to the greatest spin delocalization to the iodine centers on the periphery of the dimerIn this vignette, we present results for a ferrous dimer that acts as a text book example of the situation in which there is clear competition between intra- and interdimerexchange interactions. The latter prevail at low temperature and lead to genuine spontaneous long range 3D-order in zero field as discerned via the Mössbauer Effect.This outcome stems from the hydrogen bonded exchange network of the structure illustrated on the next slide.

“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

EXTENSIVELY HYDROGEN BONDED CHAINS OF DI-CHLORO BRIDGED NEUTRAL FERROUS DIMERS (HEREAFTER 1) BASED ON

MER-Fe(II)(H2O)3CL3 CHROMOPHORES

The neutral structure(3) of 1 is stabilized with accompanying 1,4-dimethylpiperazinium dications and “free”chloride anions not shown for purposes of clarity.

[----- = Cl–H HYDROGEN BONDS]

(3)S. I. Troyanov, M. Feist, and E. Kemnitz, Z. Anorg. Allg. Chem., 625, 806 (1999).

1

“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

Best fit (HDVV model) J/kB= ~-0.5K (-0.35cm-1)

The intradimer antiferromagnetic exchange leads to a set of five S Total states spanning ST = 0, 1, 2, 3, 4, where the separation (2J) of the ground singlet, ST = 0, and first excited state, a triplet, ST=1 for the case of 1 is ~ 1 K.

“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

From 80K to 5K, the magnetic moment of 1 gradually decreases from near the spin only value of high spin Fe2+ (4.9/Fe) to~ 3/Fe, a factor of ~1.6. This behavior is typical of weak intra-dimer antiferromagnetic exchange, J/kB -0.5K for 1. However, below 5K, 1’s magnetic moment/Fe further decreases rapidly to ~ 0.6 at 1.4K, a factor of 6!

0.6

125 HzHAC=1 Oe

“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

Magnetic hyperfine splitting of the zero field Mössbauer spectrum of 1 essentially coincident with the inflection point (~ 4.3 K) in ’ vs T is evident for T 5K. At 1.49 K, the nuclear Zeeman splitting is fully resolved and corresponds to an internal field of 14 T. The long range 3-dimensional magnetic order suggested by these observations is further confirmed by dual phase AC susceptibility (1 Oe, 125 Hz) measurements that indicate that 1 has an uncanted antiferromagnetic ground state, i.e. = 0.

Rapidly

Relaxing

Paramagnet

Saturated

Uncanted

Antiferromagnet

“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

Definitive evidence for the antiferromagnetic nature of the system’s magnetic ground state comes from the observation of a well defined metamagnetic phase transition at 1.95 T in the (DC) field dependence of the AC susceptibility [4] at 1.97 K, cf: to similar behavior for anhydrous FeCl2 for which Hcritical 1T at 4.2 K. One concludes that the inter-dimer (hydrogen bonding based) super-exchange for 1 at T5 K is of sufficient magnitude as to lead to long range (cooperative 3d) order “before” the moments of individual dimers “die out” with decreasing T owing to their intrinsic (intra-dimer) antiferromagnetic exchange. [4] A. J. Van Duyneveldt, J. Appl. Phys., 53, 8006 (1982).

“Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal Chemistry@Springer-Verlag 2009”

It seems evident that the Mössbauer Effect clearly provides a facile tool for discerning genuine magnetic order. This is especially so for cases such as the present where the crossover from seemingly simple antiferromagnetcally coupled dimers to long range order is quite subtle in the context of conventional susceptibility methods. In addition, as an experimental technique, it is quite complementary to other zero field techniques, e.g. constant pressure heat capacity and powder neutron diffraction measurements. There is little doubt that it will continue as an invaluable perhaps first choice method for detailed investigations of highly correlated electron spin behavior in iron based systems.

Conclusion