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Transition Metal Complexes and Radical Anion Salts of 1,10-Phenanthroline Derivatives Annulated with a 1,2,5-Tiadiazole and 1,2,5-Tiadiazole 1,1-Dioxide Moiety: Multidimensional Crystal Structures and Various Magnetic Properties

Advances in the molecular variety and the elucidation of the physical properties of 1,10-phenanthroline annulated with 1,2,5-thiadiazole and 1,2,5-thiadiazole 1,1-dioxide moieties have been achieved, and are described herein. A 1,2,5-thiadiazole compound, [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (tdap), was used as a ligand to create multidimensional network structures based on S•••S and S•••N intermolecular interactions. A 1,2,5-thiadiazole 1,1-dioxide compound, [1,2,5] thiadiazolo[3,4-f][1,10]phenanthroline, 1,1-dioxide (tdapO2), was designed to create a stable radical anion, as well as good network structures. Single crystal X-ray structure analyses revealed that transition metal complexes of tdap, and radical anion salts of tdapO2 formed multidimensional network structures, as expected. Two kinds of tdap iron complexes, namely [Fe(tdap)2(NCS)2] and [Fe(tdap)2(NCS)2]•MeCN exhibited spin crossover transitions, and their transition temperatures showed a difference of 150 K, despite their similar molecular structures. Magnetic measurements for the tdapO2 radical anion salts revealed that the magnetic coupling constants between neighboring radical species vary from strongly antiferromagnetic (J = −320 K) to ferromagnetic (J = 24 K), reflecting the differences in their π overlap motifs.


Introduction
The electrical and magnetic properties of molecular crystals have been studied extensively, and various molecule-based conductors [1][2][3][4][5][6][7], superconductors [6,[8][9][10][11][12][13][14], and magnetic materials [15][16][17][18][19][20][21][22][23][24][25][26][27] have been synthesized to date. The research has been characterized by the enhancement of dimensionality in intermolecular interactions. As a result of the major efforts to enhance the dimensionality of intermolecular interactions, heterocyclic sulfur nitrogen (SN) compounds, which consist of nitrogen atoms and sulfur atoms, have arisen, and their solid-state properties have been investigated in relation to their crystal structures. The heterocyclic chalcogen-nitrogen compounds have attracted much attention due to their potential to form a multidimensional network structure in their crystals, which involve X•••N and X•••X (X = S, Se, Te) contacts and π-overlaps. Furthermore, some of these compounds are known to be radical species without any protecting groups. These features are believed to bring about the unique chemical and physical properties of these materials, such as the high-T c magnetic orderings, high conductivities and drastic structural phase transitions (see [28] and references therein). Although the intermolecular interactions are weaker than those of other heterocyclic chalcogen-nitrogen compounds, such as SeN and TeN compounds, various structures of heterocyclic SN compounds have been reported due to the convenience of their synthesis [28][29][30][31][32][33].
The synthesis of a closed-shell SN compound, [1,2,5]thiadiazolo [3,4-f] [1,10]phenanthroline (tdap, Scheme 1a), was reported in 2006 [34]. Using this compound as a ligand, the intermolecular interactions and electron spins which are the remarkable features of SN radicals can be separated into the 1,2,5-thiadiazole moieties and the transition metal ions, respectively. By this method, the stability can be greatly improved, whilst simultaneously maintaining the open shell structure. In this study, a 1,2,5-thiadiazole moiety is used to introduce the intermolecular interaction to transition metal ions which have a large quantum spin number.
In the present paper, we describe the crystal structures and spin-crossover transitions of tdap transition metal complexes, and the crystal structures and magnetic properties of radical anion salts of tdapO 2 .

Transition Metal Complexes of [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline
The synthesis of [1,2,5]thiadiazolo [3,4-f] [1,10]phenanthroline (tdap, Scheme 1a) was reported in 2006 by Conte et al. [34]. They reported the luminescent properties of the Eu III complex with the ligand in 2008 [49], and the photoluminescence and electroluminescence of the Tb III complex in 2011 [50]. In addition, they reported the photonuclease activity of the Fe II complex in 2010 [51]. In these papers, the crystal structures of these complexes were also reported. Thus there was no intermolecular interaction found, and the properties were discussed as single molecule features. Despite this report, we expected that the thiadiazole moiety of this ligand would have potential to form intermolecular interactions and would be a good building block for molecule-based magnets. In this chapter, we describe the crystal structures and intermolecular interactions of first-row transition metal complexes of tdap. Among them, the crystal structures and magnetic properties of two spin crossover complexes are discussed with emphasis on the intermolecular interactions and molecular structures. In this chapter, 10 [1,2,5]thiadiazolo [3,4-f] [1,10]

phenanthroline (tdap)
The electrochemical measurement of tdap in dimethyl sulfoxide (DMSO) has been reported, and revealed a redox peak in the reduction range (E 1/2 = −1.46 V vs. a normal hydrogen electrode (NHE)) [51]. To compare the acceptor ability to the related compound tdapO 2 described in a later section, the electrochemical measurement in acetonitrile (MeCN) was carried out (E 1/2 = −1.93 V vs. Fc/Fc + Figure 1, where Fc is ferrocene). These results suggest that tdap has poor acceptor ability.  [48]. Copyright 2013 American Chemical Society.

Synthesis of Transition Metal Complexes of tdap
Single crystals of transition metal complexes of tdap were obtained by the slow diffusion method using an H-shaped glass cell purged with N 2 gas [52]. Crystal solvent-free transition metal complexes [Fe(tdap) 2 (NCS) 2 ] (black blocks) [53] and [Co(tdap) 2

Spin-Crossover Complexes of tdap
The behavior of SCO transitions is known to be greatly affected by intermolecular interactions. The magnetic properties and crystal structures of two SCO complexes of tdap are discussed in this study. The non-solvated [Fe(tdap) 2 (NCS) 2 ] is reported to exhibit a SCO transition at 320 K [53].  Table 1. The transition was accompanied by an expansion of the Fe-N distances in the same manner as for previously reported SCO complexes [55].  Both in the HS and LS states, the space groups were P2 1 /n, and there was a 5.5% difference in unit cell volume between the two states. This change results not only from the thermal expansion of the crystal lattice, but also from the expansion of the Fe-N distances upon the SCO transition. The crystal structure of [Fe(tdap) 2 (NCS) 2 ]•MeCN, measured at 120 K, is shown in Figure 2b. In the LS state, the molecular packing exhibits S(1)•••N(11) contacts (3.017(4) Å: blue broken lines in Figure 2b), which are shorter than the sum of van der Waals (VDW) radii (3.35 Å), and weak S(2)•••S(4) (3.5911(7) Å: red broken lines in Figure 2b) contacts, which are almost the same as the sum of VDW radii (3.60 Å). Hereafter, the VDW radii given by Bondi were used (C: 1.75 Å; Cl: 1.75 Å; N: 1.55 Å; O: 1.50 Å; S: 1.80 Å) [56]. This weak S(2)•••S(4) contact forms a one-dimensional (1D) structure for the [Fe(tdap) 2 (NCS) 2 ] complexes, while the S•••N short contacts quench the intermolecular interactions between complexes. After the transition to the HS state, the S(2)•••S(4) contacts show a 2.5% expansion, while the S(1)•••N(11) distance shows a 2.4% reduction. As a result, the S(2)•••S(4) distances elongated to 3.6805(8) Å, which is longer than the sum of the VDW radii, and the complexes showed less interaction in the HS state.
Magnetic susceptibility measurements of [Fe(tdap) 2 (NCS) 2 ]•MeCN were performed under 0.5 T, in the temperature range of 2-400 K. Both the heating and cooling processes were performed to confirm the non-existence of structural change due to the evaporation of crystal solvent. The fact that the same profiles were observed in both processes suggests that no evaporation occurred even at 400 K. The paramagnetic susceptibility (χ p ) of the complex was calculated with a diamagnetic susceptibility (χ dia ) that was obtained by assuming that the temperature (T) dependence of χ p followed the Curie law at low temperature. The temperature dependence of χ p of [Fe(tdap) 2 (NCS) 2 ]•MeCN is shown in Figure 3. Since there is no observable thermal hysteresis in the SCO transition, only the heating process is shown. At low temperature, below 120 K, the value of χ p T is nearly constant (0.13 emu mol −1 K), though the spin state is expected to be S = 0. This is probably partially due to the presence of the HS state and/or contamination of the paramagnetic complex. Above 150 K, χ p T shows a gradual increase, and reaches 3.57 emu mol −1 K at 400 K. This value is larger than the theoretical spin-only value for a 5 T 2g ground state (3.0 emu mol −1 K with g = 2, where g is a g-factor), indicating spin-orbital coupling.  [53]. Adapted by permission of The Royal Society of Chemistry).

[Fe(tdap) 2 (NCS) 2 ]
The solvent-free [Fe(tdap) 2 (NCS) 2 ] was crystallized in the Pna2 1 space group. The molecular structure and selected bond lengths of solvent-free [Fe(tdap) 2 (NCS) 2 ] are shown in Figure 4a and Table 1   The comparison of the crystal structures in the HS state and LS state reveals several characteristic differences. It is notable that the N(10)-C(26) distance (for the NCS ligand) in the HS state is extremely short (see Figure 4a), presumably due to chemical pressure caused by the intermolecular contacts. The N-C(S) bond lengths at 400 K (1.117(9) Å for N(9)-C(25) and 1.055(11) Å for N(10)-C(26)) were 3.6% and 9.0% shorter than those at 173 K (1.159(5) Å for N(9)-C (25) and N(10)-C(26)), while [Fe(phen) 2 (NCS) 2 ] [54] and [Fe(tdap) 2 (NCS) 2 ]•MeCN exhibit a slight increase of 1.6% and a decrease of 0.6% in the N-C(S) distances, respectively. A comparison between the molecular structures of the solvated and non-solvated forms indicates that the large shrinkage in the latter would be caused by its characteristically short S•••S contacts. It is hard to clearly rationalize this difference, but the expansion of the FeN6 core could be balanced by such shrinkages in the non-solvated [Fe(tdap) 2 (NCS) 2 ].
Magnetic susceptibility measurements of [Fe(tdap) 2 (NCS) 2 ] were performed under 0.5 T, in the temperature range of 2-400 K. The χ p of the complex was calculated with a χ dia that was obtained by assuming that the temperature dependence ofχ p followed the Curie law. The temperature dependence of χ p for [Fe(tdap) 2 (NCS) 2 ] is shown in Figure 3. Below 150 K, the value of χ p T is nearly constant (0.21 emu mol −1 K), which is probably extrinsic. Above 180 K, χ p T shows a gradual increase, and reaches 2.56 emu mol −1 K at 400 K. This value is smaller than the theoretical spin-only value for a 5 T 2g ground state (3.0 emu mol −1 K with g = 2), indicating an incomplete transition. It is notable that there is no thermal hysteresis in the SCO transition in [Fe(tdap) 2 (NCS) 2 ], despite the intermolecular contacts in this compound. The unsubstituted 1,10-phenanthroline complex [Fe(phen) 2 (NCS) 2 ] is known to exhibit a steep SCO transition at 177 K without hysteresis [54]. Since the FeN6 geometry in [Fe(tdap) 2 (NCS) 2 ] is very similar to that in [Fe(phen) 2 (NCS) 2 ], the intermolecular contacts in [Fe(tdap) 2 (NCS) 2 ] are considered to bring about a high temperature shift of more than 100 K in the SCO transition. As described above, the intermolecular interactions of [Fe(tdap) 2 (NCS) 2 ] disturb the molecular expansion of the SCO transition. As a result, the expanded structure in the HS state is destabilized, and the LS state is maintained to a high temperature. Light-induced excited spin-state trapping (LIESST) experiments were performed under 0.5 T, in the temperature range of 5-120 K. An Hg-Xe lamp (550 nm, 1.5 mW cm −2 ) was used as a light source.
The light, passing through infrared (IR) and green filters, was guided via an optical fiber into the superconducting quantum interference device (SQUID) magnetometer. The sample was placed on the edge of the optical fiber. The thermal relaxation of the paramagnetism induced by photo-irradiation at 5K (Δχ p T) is shown in Figure 5. Light irradiation brings about a magnetization increase, but is saturated to a small value that is only 1.3% of the theoretical value for a complete LS to HS transition. Since [Fe(tdap) 2 (NCS) 2 ] appears as black crystals, only the surface molecules exhibit the spin transition. Upon heating, the photo-induced magnetization disappears at 80 K; this temperature is higher than that of the unsubstituted phenanthroline complex (55 K) [54].

Crystal Structures of tdap Transition Metal Complexes
The crystal structure of the crystal solvent-free cobalt complex [Co(tdap) 2 (NCS) 2 ] is shown in Figure 6. The [Co(tdap) 2 (NCS) 2 ] complexes are located on a 2-fold rotation axis. The unit cell contains two right-handed and two left-handed enantiomers of this chiral complex. The packing motif of [Co(tdap) 2 (NCS) 2 ] is much different from that of the crystal solvent-free iron complex [Fe(tdap) 2 (NCS) 2 ] ( Figure 4). There are no short intermolecular contacts, although this crystal does not contain crystal solvents which could quench the intermolecular interaction between neighboring complexes as is observed in [Fe(tdap) 2 (NCS) 2 ]•MeCN. The molecular arrangement of this crystal seems to be governed only by VDW forces and a small π-interactions (interplanar distances of ~3.47 Å) between tdap moieties.   Figure 8. In the crystal of the Ni complex, no short intermolecular interaction is found, either between complexes or between a complex and an MeCN molecule.
Magnetic susceptibility measurements of [M(tdap) 2 (NCS) 2 ]•MeCN (M = Mn, Co, Ni, Zn) were performed under 0.5 T, in the temperature range of 2-300 K. Curie paramagnetic behavior was found in the Mn, Co and Ni complexes, and the Zn complex exhibited diamagnetism. The measured Curie constants of the Mn, Co, Ni and Zn complexes at 300 K were 4.37, 2.95, 1.22 and 0.0057 emu mol −1 K, respectively, which are comparable to (Mn) or higher than (Co, Ni) the theoretical spin-only value. The higher value in the Co and Ni complexes was due to the spin-orbit coupling. Furthermore, the stronger magnetic anisotropy of the Co and Ni ions brought about a gradual decrease of the χ p T value of the Co complex, and a small increase of the χ p T value of the Ni complex.  There are two crystallographically nonequivalent thiocyanate ions. While one of the thiocyanate ions has a positional disorder, the other ion is fixed on a certain position, maybe due to the intermolecular interaction described above. It appears that the disordered thiocyanate ion simply fills a vacant space.  [53]. Adapted by permission of The Royal Society of Chemistry.

Dinuclear Copper Complexes
The crystal structure of the monovalent copper complex [Cu 2 (tdap) 2 (NCS) 2 ] is shown in Figure 11. Two monovalent Cu ions are bridged by two thiocyanate ions. The coordination geometry around Cu ions is distorted tetrahedral, reflecting the d 10 electron configuration of Cu I . The tdap moieties form a π stacked column, with an interplanar distance of 3.50 Å, in the direction of the a axis. These columns are bridged by the coordination bonds of copper-thiocyanate-copper, and the [Cu 2 (tdap) 2 (NCS) 2 ] complexes form a zig-zag sheet structure.
The crystal structure of the divalent copper complex [Cu 2 (tdap) 2 (NCS) 4 ] is shown in Figure 12. Two Cu ions are bridged by two thiocyanate ions. In contrast to [Cu 2 (tdap) 2 (NCS) 2 ], an additional thiocyanate ion is coordinated to a Cu ion. The geometry around a Cu II ion is square pyramidal, which is formed by four squarely coordinated nitrogen atoms from a tdap and two thiocyanate ions, and a sulfur atom from a thiocyanate ion on a perpendicular axis to the square. There are short contacts between the sulfur atoms of thiocyanate ions and tdap (3.3632(7) and 3.4073 Å) which form a ladder structure. Two Cu ions face each other across the ladders. The distance between intermolecular Cu ions, which is shown as broken lines in Figure 12, is 3.5812(14) Å.

Radical Anion Salts of [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 1,1-dioxide
The molecule tdapO 2 is designed to possess a stable radical anion species, due to the strong electron-withdrawing property of the thiadiazole dioxide moiety [36,[57][58][59], which enhances the acceptor ability of tdapO 2 . In addition, the phenanthroline and thiadiazole dioxide moieties at the molecular ends are expected to operate as a ligand and/or a proton acceptor, which can realize multi-dimensional interactions (Scheme 1b). In this chapter, we describe the electrochemical properties of tdapO 2 first. Then we describe the multi-dimensional network structures and magnetic properties of the tdapO 2 radical anion salts, which were reported previously [47,48], and a novel radical anion salt [CoCp 2 ]•tdapO 2 .
The crystal structure of tdapO 2 consists of a 2D layer formed by C-H•••N hydrogen bonds, as shown by the broken lines in Figure 13c. Figure 13d shows a side view of the layered structure, where the interlayer arrangement includes a S-O•••H hydrogen bond, and very partial π-overlap. Figure 13b suggests the bending of the tdapO 2 molecule (ca. 15°), which may have been due to the repulsive force between neighboring molecules caused by the out-of-plane S=O bonds. Figure 13. Molecular structure (a,b) and crystal structure (c,d) of tdapO 2 . Adapted with permission from [47]. Copyright 2011 American Chemical Society. Figure 14 shows the CV of tdapO 2 , which indicates two reversible reduction peaks at -0.520 and -1.32 V vs. Fc + /Fc; these processes suggest that the mono and dianionic species of tdapO 2 are stable and the acceptor ability of tdapO 2 are comparable to those of the halogen-substituted p-benzoquinones [61][62][63][64]. It is notable that the related compound tdap exhibits very weak acceptor ability (see Figure 1). This means that the oxidation of the sulfur in the thiadiazole ring notably reduces the reduction potential. Solution EPR spectrum measurement of the reduced tdapO 2 was carried out on a CH 2 Cl 2 solution of mono-anionic tdapO 2 , which was prepared by the following method. A purple solution of reduced tdapO 2 in MeCN was prepared by potentiostatic reduction (−0.6 V vs. Ag/Ag + ) of 1 mM tdapO 2 in an MeCN solution of 100 mM TBAClO 4 . The resulting MeCN solution was then evaporated to dryness and dissolved in CH 2 Cl 2 . This CH 2 Cl 2 solution was degassed by a frozen degassing technique, and vacuum-sealed in a quartz cell. The measured and simulated EPR spectra are shown in Figure 15. The complex hyperfine structure suggests the existence of an unpaired electron that is well delocalized over the tdapO 2 skeleton. Figure 15. Experimental (red) and simulated (gray) solution EPR spectra of mono-anionic tdapO 2 . The inset shows the hyperfine coupling constants in units of mT used for the simulation, and in parentheses, the estimated spin density on the nitrogen and carbon atoms. Adapted with permission from [48]. Copyright 2011 American Chemical Society.
Theoretical fitting was carried out, and a best fit was obtained with the following parameters: g = 2.0032, two N (I = 1) with a N = 0.349 mT, two N (I = 1) with a N = 0.025 mT, two H (I = 1/2) with a H = 0.152 mT, two H (I = 1/2) with a H = 0.148 mT, and two H (I = 1/2) with a H = 0.05 mT, where I is the nuclear spin quantum number, and a N and a H are the hyperfine coupling constants for nitrogen and hydrogen, respectively. The spin distribution on the tdapO 2 radical anion was estimated from the McConell relation, a H = Q C  C and a N = Q N  N . Q C and Q N are the proportionality constants for the hydrogen-neighboring carbon, and for nitrogen, respectively [65,66].  C and  N are the spin distribution on the carbon and nitrogen, respectively. Q constants of Q C = −2.45 mT [67] for carbon of azaaromatic rings and Q N = +2.5 mT [68] for nitrogen were applied. The calculated spin densities are 0.14 and 0.01 for each of the two distinct nitrogen atoms, and 0.06 and 0.02 for the carbon atoms neighboring a hydrogen, at position 2 and 4, and at position 3 (Figure 15 inset), respectively. The positions of each spin density are proposed by comparing the obtained value with the calculated spin density of mono-anionic tdapO 2 [48].

Nonsolvated and Solvated Potassium Salts: K•tdapO 2 and KtdapO 2 •0.5MeCN
The crystal structure of nonsolvated K•tdapO 2 is shown in Figure 17a,b. Because the tdapO 2 molecules are located on a mirror plane, the molecular structure of tdapO 2 is ideally planar. The crystal structure of K•tdapO 2 consists of a 2D layer, formed by a coordination polymer chain along the a + c direction (Figure 17a), and regular π-stacking along the b axis with interplanar distances of 3.30 Å (Figure 17b). It thus seems that 2D layers are connected only by VDW force. Figure 17c,d show the crystal structure of K•tdapO 2 •0.5MeCN, which consists of a 2D layer formed by π-stacking along the a axis and a coordinate bonding chain along the c axis (Figure 17c). The 2D layers are connected by coordination bonds of MeCN molecules which are located between two alkali metal ions. The MeCN molecules of K•tdapO 2 •0.5MeCN are disordered between two K ions as shown in Figure 17c. The π-stacking chain includes a very weak alternation with interplanar distances of 3.36 and 3.42 Å. The π-overlaps between tdapO 2 molecules in these salts (Figure 18b,d) are much larger than that in the neutral tdapO 2 (Figure 13c), probably due to the exchange interactions between the radical anions.   5MeCN (c,d). Temperature dependence of χ p for K•tdapO 2 and K•tdapO 2 •0.5MeCN (e). Adapted with permission from [47] and [48]. Copyright 2011 and 2013 American Chemical Society.
The coordination geometry around the potassium ion and π-overlaps in K•tdapO 2 and K•tdapO 2 •0.5MeCN are shown in Figure 18. The π-overlaps between neighboring tdapO 2 molecules of these two salts are much larger than that of neutral tdapO 2 , probably due to the exchange interaction between radical anions. The π-overlap motifs of the nonsolvated form (Figure 18b) and the solvated form (Figure 18d) are significantly different from each other, presumably due to the geometrical difference around the potassium ions induced by MeCN coordination, as shown in Figure 18a,c.   Figure 18. Coordination geometry around the potassium ion (a,c) and π-overlaps (b,d) in K•tdapO 2 (top) and K•tdapO 2 •0.5MeCN (bottom). Adapted with permission from [48]. Copyright 2011 American Chemical Society.
The measurements of the temperature dependences of the magnetic susceptibility for K•tdapO 2 and K•tdapO 2 •0.5MeCN were performed under 3 T, in the temperature range of 2-300 K (Figure 17e). The temperature dependences of χ p of these radical anion salts were calculated with diamagnetic susceptibilities that were obtained as fitting parameters of the Bonner-Fisher model and Bleaney-Boweres model, respectively.
The χ p of K•tdapO 2 (green circles in Figure 17e) shows a gradual increase with a decrease in temperature from 300 K. After reaching a maximum at 13.5 K, χ p shows a decrease, followed by another quick increase below 6.5 K. The latter behavior is probably caused by the Curie spins on the lattice defects. The χ p values in the range of 16-300 K can be well fitted to the antiferromagnetic Bonner-Fisher model (Equation (1)), assuming the spin Hamiltonian in the zero field to be H = -2J S i •S i+1 , where J is the antiferromagnetic coupling constant, and S i and S i+1 are the monoelectronic spin operators [69][70][71]. The numerical expression is 0.25 + 0.14995x + 0.30094x 2 1 + 1.9862x + 0.68854x 2 + 6.0626x 3 (1) where x = |J|/k B T. The solid curve on the open circles in Figure 17e is the theoretical best fit of this model with g = 2.00 ± 0.05 and J/k B = −13 ± 1 K, where N A is the Avogadro's number,  B is the Bohr magneton and k B is the Boltzmann constant. The χ p of K•tdapO 2 •0.5MeCN (blue circles in Figure 17e) was smaller than that of K•tdapO 2 , reflecting the alternating nature of the π-stack column. The temperature dependence of χ p for K•tdapO 2 •0.5MeCN decreases in temperature from 300 K and forms a broad maximum around 150 K. Further cooling induces a quick increase below 10 K due to Curie defects. The behavior at the high temperature can be fitted to the Bleaney-Bowers model (Equation (2)) with the spin Hamiltonian in zero field: H = −2J S 1 •S 2 [69,72]. The numerical expression is The χ p values in the range of 200-300 K can be well fitted with following fitting parameters: g = 2.0 ± 0.1 and J/k B = −110 ± 10 K.

Mixed Valent Salts: K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2
The crystal structures of K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 were isostructural. Figure 19a,b shows the crystal structure of K•(tdapO 2 ) 2 , which consists of two crystallographically nonequivalent tdapO 2 molecules 1 (blue) and 2 (red). The bond lengths of these two tdapO 2 molecules (1 and 2) are sufficiently distinguishable (green circles in Figure 16), and clearly indicate that one molecule is neutral (1) and the other molecule is anionic (2). They form an alternating π-stacking arrangement along the a + c axis, with very similar interplanar distances of 3.29 Å but different intermolecular arrangements (i) and (ii). In a similar way, the tdapO 2 molecules in Rb•(tdapO 2 ) 2 form an alternating π-stacking arrangement with interplanar distances of 3.29 (i) and 3.31 Å (ii). As shown in Figure 19a, a potassium ion is tweezered by the phenanthroline moieties of the coplanar molecules 1 and 2 in different π-stacking columns, and is capped by the two thiadiazole dioxide moieties from both sides of the plane. These salts are in a class I mixed valence state [73], or, in other words, in a charge-ordered state-a state that has attracted much attention in recent years. Figure 19b indicates that the molecules 1 and 2 exhibit a checker-board-type charge ordering [74]. Figure 19. Crystal structure (a,b) of K•(tdapO 2 ) 2 and temperature dependence of χ p (c) for K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 . Adapted with permission from [47] and [48]. Copyright 2011 and 2013 American Chemical Society. Figure 19c depicts the temperature dependence of χ p for K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 , where the molar unit contains two tdapO 2 molecules. The behavior of K•(tdapO 2 ) 2 (green circles in Figure 19c) in the temperature range from 33 to 350 K can be fitted to the Bonner-Fisher model (Equation (1)) with the following fitting parameters: g = 1.95 ± 0.05 and J/k B = −20 ± 1 K for K•(tdapO 2 ) 2 . The behavior of Rb•(tdapO 2 ) 2 (blue circles in Figure 19c) in the temperature range from 54 to 300 K can be fitted to the Bonner-Fisher model (Equation (1)) with the following fitting parameters: g = 1.94 ± 0.06 and J/k B = −29 ± 1 K.
The |J| values of K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 are larger than that of K•tdapO 2 , though the π-stacking column in K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 includes the non-magnetic molecule 1. In general, the intermolecular magnetic exchange interaction results from cancellation between the ferromagnetic and antiferromagnetic contributions. Therefore, it is not entirely surprising that the antiferromagnetic interactions in K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 are stronger than that in K•tdapO 2 , if the latter involves a stronger ferromagnetic contribution. Below ca. 15K, the χ p values of K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 exhibit a sudden jump (Figure 20a), followed by a Curie-like behavior. The field dependence of the magnetization was measured at various temperatures. The magnetization curves (Figure 20b,c) indicate the presence of a small spontaneous magnetization below these temperatures, which is probably caused by spin canting. These are some of the highest transition temperatures among molecule-based magnetic materials that do not include transition metals [18].  (Figure 16) suggest that the valence of tdapO 2 is −1 and the composition formula is Cs 7 •(tdapO 2 ) 6 •ClO 4 . A Cs ion is surrounded by five oxygen atoms belonging to five tdapO 2 and four nitrogen atoms belonging to three tdapO 2 . The other Cs ion is surrounded by six oxygen atoms belonging to six tdapO 2 and eight oxygen atoms (whose occupancy is 0.5) belonging to two ClO 4 ions. A notable point is that six tdapO 2 radical anions are located on a so-called "Kagomé lattice," in which antiferromagnetically interacted spins form a frustrated system [75]. They also form a strongly alternating π-stacking arrangement along the c axis, with interplanar distances of 3.13 (i) and 3.29 Å (ii). Figure 21. Crystal structure (a,b) and temperature dependence of χ p (c) for Cs 7 •(tdapO 2 ) 6 •ClO 4 . Adapted with permission from [48]. Copyright 2013 American Chemical Society. Figure 21c depicts the temperature dependence of χ p for Cs 7 •(tdapO 2 ) 6 •ClO 4 , where the molar unit contains one tdapO 2 molecule. With the decrease in temperature from 300 K, χ p shows a gradual decrease. After reaching a minimum around 100 K, the value of χ p is maintained down to 30 K, and then shows another quick increase. The latter behavior is probably caused by the Curie spins on the lattice defects, whose Curie constant is calculated as 0.0037 emu mol −1 K. The behavior of Cs 7 •(tdapO 2 ) 6 •ClO 4 in the temperature range from 30 to 300 K can be fitted to the Bleaney-Bowers model. The best fit was obtained with the following fitting parameters: g = 2.0013 (fixed) and J/k B = −310 ± 10 K for Cs 7 •(tdapO 2 ) 6 •ClO 4 . The g value was fixed at 2.0013, which was obtained from solid EPR measurement for a microcrystalline sample of Cs 7 •(tdapO 2 ) 6 •ClO 4 . Figure 22a,b shows the crystal structure of (NH 4 ) 2 •tdapO 2 •I, which consists of an alternating π stacking of tdapO 2 with interplanar distances of (i) 3.35 and (ii) 3.44 Å (see Figure 22b). These are longer than those observed in the alkali metal salts. The intermolecular π-overlaps, (i) and (ii), in the stacking chain are shown in Figure 23b. Both the phenanthroline and thiadiazole dioxide moieties form hydrogen bonds to different ammonium ions, indicating the proton-accepting ability of the tdapO 2 radical anion (Figure 23a). Between the stacking columns, a 2D hydrogen-bonding network is formed by NH 4 + , I − and the proton-accepting moieties of tdapO 2 . Adapted with permission from [48]. Copyright 2013 American Chemical Society.
The crystal structure of Hppda•tdapO 2 •MeCN is shown in Figure 22c,d. Because it is difficult to determine the existence of the protons by XRD analysis, due to their small electron density, the valence of tdapO 2 was confirmed to be monovalent from the bond lengths of the crystal structure ( Figure 16). This result implies that a ppda molecule is protonated and becomes a 4-aminoanilinium ion (Hppda). The geometry of the hydrogen bonds around N(5), shown in Figure 23c, also implies a protonation of N(5). The crystal structure of Hppda•tdapO 2 •MeCN consists of a regular π-stacking of tdapO 2 with interplanar distances of 3.42 Å (Figure 22d). This distance is comparable to those of (NH 4 ) 2 •tdapO 2 •I. The intermolecular π-overlap in the stacking chain is shown in Figure 23d. The π-stack columns are connected by hydrogen bondings between tdap radical anions and Hppda cations, and form a 3D hydrogen-bonding network structure.
The blue circles in Figure 22e show the temperature dependence of χ p T for (NH 4 ) 2 •tdapO 2 •I. When the temperature decreases from 300 K, χ p T exhibits a gradual increase down to 30 K. After passing a broad maximum, χ p T decreases quickly. This behavior indicates the coexistence of ferromagnetic and antiferromagnetic interactions, with the former being stronger than the latter. Since the crystal structure consists of alternated π-stacking, this temperature dependence can be interpreted in terms of a ferromagnetic dimer, with weak antiferromagnetic interdimer coupling ( [76] using where J 1 and J 2 express the intradimer ferromagnetic coupling constant, and the interdimer antiferromagnetic coupling constant, respectively, and z is the number of the nearest neighbors connected by J 2 . The solid curve on blue circles in Figure 22e is the theoretical best fit with g = 1.94 ± 0.10, J 1 /k B = 24 ± 1 K and zJ 2 /k B = −7.9 ± 0.1 K. It is clear that the tdapO 2 radical anion has the potential to yield both ferromagnetic and antiferromagnetic intermolecular interactions. The green circles in Figure 22e show the temperature dependence of χ p T for Hppda•tdapO 2 •MeCN. When the temperature decreases from 300 K, χ p T exhibits a gradual increase down to 10 K. After passing a broad maximum, χ p T decreases quickly. This behavior is similar to that of (NH 4 )•tdapO 2 •I. Since the crystal structure consists of regular π-stacking, this temperature dependence can be interpreted in terms of a ferromagnetic 1D chain with weak antiferromagnetic interchain coupling (H = −2J 1 ΣS i •S i+1 and a molecular mean-field correction) [69,71,77] using where χ p = (N A g 2 μ B 2 )/(4k B T)[N/D] 2⁄3 , N = 1.0 + 5.7979916x + 16.902653x 2 + 29.376885x 3 + 29.832959x 4 + 14.036918x 5 , D = 1.0 + 2.7979916x + 7.0086780x 2 + 8.6538644x 3 + 4.5743114x 4 , and x = J 1 ⁄(k B T). The χ' p and χ p are the magnetic susceptibility with and without mean-field correction, respectively. The parameters J 1 and J 2 express the intrachain ferromagnetic coupling constant and the interchain antiferromagnetic coupling constant, respectively, and z is the number of the nearest neighbors connected by J 2 . The solid curve on green circles in Figure 22e is the theoretical best fit with g = 1.84 ± 0.10, J 1 /k B = 5.6 ± 0.  Table S1 (Supplementary Materials). The valence of tdapO 2 could be determined as −1 from its bond length ( Figure 16). The π-overlap arrangements of [CoCp 2 ]•tdapO 2 are shown in Figure 24. The intermolecular arrangement of the tdapO 2 radical anions in this system is much different from those in the other radical anion salts. The molecular planes of tdapO 2 are not parallel. The overlapped part shows a closer interplanar distance, maybe due to the exchange interaction through π orbitals.   The temperature dependence of χ p for [CoCp 2 ]•tdapO 2 is shown in Figure 25c. With a decrease in temperature from 300 K, χ p shows a gradual increase. After reaching a maximum around 50 K, χ p shows a slight decrease, followed by another quick increase below 20 K. The latter behavior is probably caused by the Curie spins on the lattice defects. The structural study revealed that the tdapO 2 π-stack column is well separated by the diamagnetic cation [CoCp 2 ] + . The χ p values in the range of 60-300 K can be well fitted to the antiferromagnetic Bonner-Fisher model (Equation (1)). The solid curve on the circles in Figure 25c is the theoretical best fit of this model with g = 1.92 ± 0.10 and J/k B = −49 ± 5 K.

Theoretical Calculations
It is quite remarkable that the tdapO 2 radical anion salts exhibit exchange-coupling constants that vary significantly from antiferromagnetic J/k B = −310 K to ferromagnetic J/k B = 24 K values (see Table 2). Wave function-based ab initio difference-dedicated configuration interaction (DDCI) calculations for the exchange interactions of 6 different radical dimers that were found in four kinds of tdapO 2 salts were carried out [48]. The exchange coupling constants J, effective hopping integral t, on-site repulsion U, and direct exchange K are summarized in Table 2. The ferro-and antiferromagnetic contributions can be estimated by following the 2J = 2K − 4t 2 /U partitioning, with the 2K term representing the ferromagnetic contribution and the −4t 2 /U term the antiferromagnetic contribution. The U values for tdapO 2 salts are almost constant, in agreement with the finding of Rota et al. that the U values are mostly governed by building units [78]. The magnetic orbitals are the in-phase and out-of-phase linear combinations of the singly occupied MOs (SOMOs) localized on each radical ( Figure 26). The relative position of the radicals (i.e., the three-dimensional arrangement) becomes a determining factor governing the magnetic interactions reflecting the localized character of the spin densities. Table 2 shows the evolution of the J value with respect to the interplanar distance between the radical dimers. The significant dependence of the exchange coupling constant on this structural parameter is very instructive and indicates that the overlap between the monomers plays a major role in defining the magnetic character of these materials. The calculated exchange coupling constant values are in good agreement with the experimental estimates (Table 2), despite some qualitative deviations observed in weakly interacting systems.
The comparison between Hppda•tdapO 2 •MeCN and the hypothetical Hppda•tdap•MeCN (lacking oxygen atoms on the thiadiazole ring) is rather instructive. Removal of the oxygen atoms shifts the magnetic behavior from ferro-(13 K) to antiferromagnetic (−4 K). It is remarkable that removal of the electron-withdrawing oxygen atoms leads to a ca. 3800 K increase of U in the hypothetical Hppda•tdap•MeCN radical as compared to Hppda•tdapO 2 •MeCN. Such variation of U is overtaken by a significant increase of the hopping integral t (from 85 to 791 K), which drives the hypothetical Hppda•tdap•MeCN into the antiferromagnetic regime. The presence of oxygen atoms reduces the superexchange contribution (absolute value of the antiferromagnetic contribution) with competitive effects on the parameters t and U. Table 2. Interplanar distances (d int ) and magnetic exchange coupling constants (J 1 and J 2 ) from the theoretical fits of experimental data, and J calc and corresponding t, K, and U parameters from DDCI calculations performed on radical anion pairs. Adapted with permission from [48]. Copyright 2013 American Chemical Society.  [48]. Copyright 2013 American Chemical Society.

Summary
The 1,2,5-thiadiazole compound tdap was induced to transition metal complexes in an effort to enhance intermolecular interactions and form highly networked systems. As a result, some of these complexes exhibited S•••S, S•••N, or S•••X intermolecular interactions, and formed a dimer, 1D ladder, 2D layer, and three-dimensional (3D) network structure. These interactions could be classified into four types: S(tdap)•••S(tdap), S(tdap)•••X (X = S, Cl belonging to coordinated anion), S(tdap)•••N(tdap), and S(tdap)•••X (X = N, Cl, S belonging to packing molecule or anion). The packing molecules and anions tended to quench the network structure in transition metal complexes of tdap. The effect of the intermolecular interaction on the physical properties was shown in the spin-crossover complex by the shift in their transition temperatures. [Fe(tdap) 2 (NCS) 2 ]•MeCN and [Fe(tdap) 2 (NCS) 2 ], underwent an SCO transition whose critical temperatures (T c ) were 210 and 315 K, respectively. A significant shift of transition temperature was found in solvent-free [Fe(tdap) 2 (NCS) 2 ], and may have been due to the chemical pressure caused by strong intermolecular interactions.
The 1,2,5-thiadiazole dioxide compound tdapO 2 was designed as a stable electron acceptor molecule with coordination sites. The electrochemistry of this compound indicated its good acceptor ability. The chemical and electrochemical reduction successfully gave 8 kinds of radical anion salts. These salts formed highly networked structures governed by effective coordination or hydrogen bonds. Most of the radical anion salts exhibited 1D magnetic behavior with various magnetic coupling constants that ranged from strong antiferromagnetic (−320 K) to ferromagnetic (24 K). Mixed-valent salts K•(tdapO 2 ) 2 and Rb•(tdapO 2 ) 2 showed magnetic ordering at low temperature, indicating the existence of considerable intercolumnar magnetic interactions in these salts.
Whereas the intermolecular interaction and physical properties of 1,2,5-thiadiazole compounds have been extensively reported on, for many systems, the solid state physical properties of 1,2,5-thiadiazolo 1,1-dioxide compounds have just started to be investigated. As shown in this review, 1,2,5-thiadiazole 1,1-dioxide compounds exhibit unique properties, such as coordination ability, proton acceptor ability, electron acceptor ability, and stability of radical anion species, with properties very different from those of 1,2,5-thiadiazole compounds. We expect the 1,2,5-thiadiazole 1,1-dioxide unit to form a new class of compounds which show exotic properties similar to those achieved for other heterocyclic chalcogen-nitrogen compound, such as thiadiazole, dithiazole, dithiadiazole etc.