Spin States of Highly Deformed Iron(III) Porphyrin Complexes Studied by 57 Fe Mössbauer Spectroscopy Mikio Nakamura a,b,c and Masashi Takahashi d a Department of Chemistry, School of Medicine, Toho University Ota-ku, Tokyo 143–8510, Japan b Research Center for Materials with Integrated Properties, Toho University Funabashi, Chiba , Japan c Division of Chemistry, Graduate School of Science, Toho University Funabashi, Chiba , Japan d Department of Chemistry, Faculty of Science, Toho University Funabashi, Chiba , Japan “Gütlich, Bill, Trautwein: Mössbauer Spectroscopy and Transition Metal 2009”

Ref. 1. M. Nakamura, Coord. Chem. Rev. 250 (2006) 2271–2294. Elucidation of the electronic structures and spin states of iron porphyrin complexes is of importance to understand the function of naturally occurring heme proteins. A number of investigations have been carried out to this end using many physicochemical methods. Among them iron-57 Mössbauer spectroscopy is a powerful and appropriate tool. The spin states of iron(III) in porphyrin complexes are controlled by the nature and number of the axial ligands through the strength of the ligand field splitting (Fig. 1). The deformation of the porphyrin ring, which induces certain specific interactions between the iron d orbitals and the porphyrin ring, also has considerable influence on the spin state [ref. 1]. A number of naturally occurring heme proteins exhibit porphyrin ring deformation. Hence the elucidation of the deformation effect is an important subject. Two modes of deformation are well- known: ruffle and saddle (Fig. 2), which result in different effects on the electronic configuration. In this paper we will focus mainly on Fe III -OETPP complexes, which adopt the saddled deformation. The abbreviations of the porphyrins and ligands appearing in this paper are listed in the last slide. low spin state S = 1/2 high spin state S = 5/2 intermediate spin state S = 3/2 Introduction: spin state and deformation of porphyrin ring ruffled deformationsaddled deformation Fig. 2 Two modes of deformation of porphyrin ring: atoms shown by open circles are above the least square plane, and those by the filled circles are below the plane. Fig. 1. Spin states adopted by Fe(III)-porphyrin complexes d x 2 -y 2 dz2dz2

Spin states of Fe(III) porphyrin complexes Fig. 3 shows the spectra of saddle-type Fe(III) OETPP complexes: [Fe(OETPP)Cl], [Fe(OETPP)(thf) 2 ]ClO 4 and [Fe(OETPP)(Him) 2 ]ClO 4. [Fe(OETPP)Cl] has a small quadrupole splitting (  E Q ) value and is assigned to the S = 5/2 state, while [Fe(OETPP)(Him) 2 ]ClO 4 has a larger  E Q value and a rather small isomer shift (  ) value corresponding to an S = 1/2 state. [Fe(OETPP)(thf) 2 ]ClO 4 shows a very large  E Q and rather large  values, indicating a large imbalance in d electron population, and is assigned to the S = 3/2 state. Five-coordinate porphyrin complexes with an axial halide ligand usually show the S = 5/2 state. Interestingly the saddled OETPP complex with an iodide ion in the axial position has a large  E Q value (3.05 mm s –1 at 77 K), indicating the S = 3/2 state [ref. 2]. This demonstrates that control of the spin state using the axial ligand is easier in non-planar porphyrin complexes. Indeed the porphycene complex, [Fe(EtioPc)I] also adopts the S = 3/2 state [ref. 3]. Ref. 2. M. Nakamura et al., Chem. Commun., (2002) 1198–1199. Ref. 3. Y. Ohgo et al., Inorg. Chem., 41 (2002) 4527–4529. [Fe(OETPP)Cl] S = 5/2 [Fe(OETPP)(thf) 2 ]ClO 4 S = 3/2 [Fe(OETPP)(Him) 2 ]ClO 4 S = 1/2 Fig Fe Mössbauer spectra of OETPP complexes at room temperature in different spin states.

Spin states of [Fe(OETPP)L 2 ]ClO 4 L = Him,  = 0.18,  E Q = 1.82 mm s –1 S = 1/2 L = dmap,  = 0.19,  E Q = 2.21 mm s –1 S = 1/2 L = py,  = 0.32,  E Q = 2.76 mm s –1 S = 3/2–1/2 L = 4-CNpy,  = 0.37,  E Q = 3.26 mm s –1 S = 3/2 L = thf,  = 0.41,  E Q = 3.65 mm s –1 S = 3/2 Fig. 4 demonstrates that the ligand field strength of the axial ligand L determines the spin state. Strongly splitting ligands [imidazole (Him) and 4- dimethylaminopyridine (dmap)] lead to the pure S = 1/2 state, while the weakly splitting ligand tetrahydrofuran (thf) gives a pure S = 3/2 spin state. Intermediate strength ligands such as pyridine (py) and 4-cyanopyridine (4-CNpy) result in new spin-crossover complexes as discussed later [ref. 4]. Interestingly the importance of the ring deformation is also confirmed in the case of the ruffled deformation: [Fe(TEtPrP)(thf) 2 ]ClO 4 also has the S = 3/2 state (  = 0.24 and  E Q = 3.80 mm s –1 ) [ref. 5]. Fig. 4 Mössbauer spectra at room temperature of six- coordinate complexes [Fe(OETPP)L 2 ]ClO 4. Ref. 4. T. Ikeue et al, Angew. Chem. Int. Ed. 40 (2001) 2617 – Ref. 5. T. Sakai et al., J. Am. Chem. Soc., 125 (2003) –

Spin-crossover in [Fe(OETPP)L 2 ]ClO 4 (L = py, 4-CNpy) Fig. 5 Mössbauer spectra of py and 4-CNpy complexes at room temperature and 77 K. The Mössbauer spectra of 4-CNpy and py show very interesting temperature dependence [ref. 4]. In both complexes the spectra change as the temperature is lowered. The 4-CNpy complex exhibits a new doublet below 230 K and the relative intensities for the site increase on decreasing the temperature. The  and  E Q values of the new site (blue) are 0.20 and 2.70 mm s –1 at 77 K, while those of the other site (green) are 0.57 and 3.03 mm s –1. This clearly indicates that two spin states co-exist at 77 K and implies a spin-crossover between S=3/2 and S=1/2. Although no new peak is observed in the py complex, both  and  E Q values decrease on lowering the temperature (Fig. 8 in a later slide), reaching values of 0.25 and 2.29 mm s –1, respectively at 77 K. This is obviously the low spin state. Thus the py complex is also a spin-crossover complex. The difference in the Mössbauer behaviour of the complexes is due to the time scale of the spin-crossover transition.

Magnetic moments and 13 C nmr chemical shifts of [Fe(OETPP)L 2 ]ClO 4 Fig. 6. Temperature dependence of magnetic moments of [Fe(OETPP)L 2 ]ClO 4 in the crystalline state (a) and in CH 2 Cl 2 solution (b). Fig. 7. Temperature dependence of 13 C chemical shifts of the meso 13 C atoms in CD 2 Cl 2 solution. Spin-crossover in py and 4-CNpy complexes is confirmed by other physicochemical methods [ref.4]: the magnetic moments of py and 4-CNpy complexes are definitely those of spin-crossover complexes (Fig. 6). Interestingly the magnetic moments determined by the Evans method in CH 2 Cl 2 indicate that spin-crossover occurs in the py complexes (Fig. 6 inset). Furthermore, the 13 C chemical shifts of the meso carbon atoms in CD 2 Cl 2 also show spin- crossover for the py complex (Fig. 7).  trs H and  trs S of the py complex are estimated to be 16.9 kJ mol –1 and 66.6 J K –1 mol –1 from the chemical shift values. Thus spin-crossover between intermediate and low spin states in the py and 4-CNpy complexes is definite. L = Him L = dmap L = py L = 4-CNpy L = thf L = 4-CNpy L = py L = Him L = dmap

Spin states of [Fe(OMTPP)L 2 ]ClO 4 OMTPP-DMAP (S = 1/2) OMTPP-Py (S =1/2) OETPP-Py (S=3/2– 1/2) OETPP-DMAP (S = 1/2) We extend the discussion to the methyl analogues [Fe(OMTPP)L 2 ] + with py and dmap [ref. 6]. Mössbauer spectra indicate that both py and dmap complexes maintain the S = 1/2 state over the temperature range 77 – 300 K (Fig. 8), and this is confirmed by SQUID magnetometry (Fig. 9). These results unexpectedly suggest that the spin states in the OMTPP complexes are quite different from those of the structurally related OETPP complexes. Furthermore, the magnetic moments measured for the solution samples confusingly show that the OMTPP-py complex behaves as a spin-crossover complex just like the OETPP-py complex [ref. 7]. Ref. 6. Y. Ohgo et al., Eur. J. Inorg. Chem. (2004) 798–809. Ref. 7. T. Ikeue et al., Inorg. Chem. 42 (2003) 5560–5571. Fig. 8 Temperature dependence of  E Q of OMTPP and OETPP complexes. Fig. 9 Temperature dependence of magnetic moments of OMTPP and OETPP complexes.

V = Å 3 Fe–N ax = Å Fe–N p = Å d = g cm –3 V = Å 3 Fe–N ax = Å Fe–N p = Å d = g cm –3 V = Å 3 Fe–N ax = Å Fe–N p = Å d = g cm –3 V = Å 3 Fe–N ax = Å Fe–N p = Å d = g cm –3 [Fe(OMTPP)(py) 2 ]ClO 4 [Fe(OETPP)(py) 2 ]ClO 4 Origin of difference in spin-crossover behaviour The key is the diference in the molecular structures, especially in the cavity around the axial ligand [ref. 6]. While the Fe–N ax lengths of OMTPP-py hardly change with temperature, those of OETPP-py contract on lowering the temperature. This difference is induced by a difference in the molecular packing: OETPP-py molecules are more loosely packed than OMTPP-py molecules. This leads to a large contraction of the cavity size (V) of OETPP-py on cooling. Thus we can conclude that the large cavity around the axial ligands is essential and important for the spin- crossover process. Fig. 10 Temperature-dependent orientation change of the pyridine ligands in the cavities of [Fe(OMTPP)(py) 2 ]ClO 4 and [Fe(OETPP)(py) 2 ]ClO 4 from 298 K (left) to 80 K (right).

Abbreviations porphyrins (OMTPP)H 2 2,3,7,8,12,13,17,18-octamethyl- 5,10, 15,20-tetraphyenylporphyrin (OETPP)H 2 2,3,7,8,12,13,17,18-octaethyl-5,10, 15,20-tetraphyenylporphyrin (TEtPrP)H 2 5,10,15,20-tetrakis(1-ethylpropyl)- porphyrin axial ligands (EtioPc)H 2 2,7,12,17-tetraethyl-3,6,11,18- tetramethylporphycene