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Article

First Molecular Superconductor with the Tris(Oxalato)Aluminate Anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, and Isostructural Tris(Oxalato)Cobaltate and Tris(Oxalato)Ruthenate Radical Cation Salts

by
Toby James Blundell
1,
Michael Brannan
1,
Joey Mburu-Newman
1,
Hiroki Akutsu
2,
Yasuhiro Nakazawa
2,
Shusaku Imajo
3 and
Lee Martin
1,*
1
School of Science and Technology, Nottingham Trent University, Clifton Lane, Clifton, Nottingham NG11 8NS, UK
2
Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama-cho, Toyonaka, Osaka 560-0043, Japan
3
The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581, Japan
*
Author to whom correspondence should be addressed.
Magnetochemistry 2021, 7(7), 90; https://doi.org/10.3390/magnetochemistry7070090
Submission received: 21 May 2021 / Revised: 11 June 2021 / Accepted: 18 June 2021 / Published: 22 June 2021
(This article belongs to the Special Issue Perspectives on Molecular Materials—A Tribute to Professor Peter Day)
Browse Figures
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Abstract

:
Peter Day’s research group reported the first molecular superconductor containing paramagnetic metal ions in 1995, β″-(BEDT-TTF)4(H3O)Fe(C2O4)3·C6H5CN. Subsequent research has produced a multitude of BEDT-TTF-tris(oxalato)metallate salts with a variety of structures and properties, including 32 superconductors to date. We present here the synthesis, crystal structure, and conducting properties of the newest additions to the Day series including the first superconductor incorporating the diamagnetic tris(oxalato)aluminate anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, which has a superconducting Tc of ~2.5 K. β″-(BEDT-TTF)4(H3O)Co(C2O4)3·C6H5Br represents the first example of a β″ phase for the tris(oxalato)cobaltate anion, but this salt does not show superconductivity.

Graphical Abstract

1. Introduction

The first paramagnetic superconductor, β″-(BEDT-TTF)4(H3O)Fe(C2O4)3·C6H5CN, was discovered in 1995 by the group of Professor Peter Day at the Royal Institution of Great Britain [1]. The ability of tris(oxalato)metallate(III) anions, M(C2O4)33−, to bridge through oxalate ions with monocations or metal(II) ions and form 2D sheets opened the door to a huge variety of structures and properties in radical cation salts with BEDT-TTF [2]. This family of salts includes not only paramagnetic superconductors, but also a ferromagnetic metal [3], antiferromagnetic semiconductor [4], and proton conductor [5,6].
Most of the reported salts in the BEDT-TTF-tris(oxalato)metallate family are 4:1 salts having the formula (BEDT-TTF)4(A)M(C2O4)3·G. The lattice consists of cation layers of BEDT-TTF alternating with anion layers where hydrogen bonding between the terminal ethylene groups of BEDT-TTF and the anion layer determine the donor molecule packing arrangement. The anion layers are built up of M and A bridged by oxalate ligands to form a honeycomb with guest molecules, G, contained within the hexagons.
The most widely studied 4:1 salts in this “Day series” are the β″ salts, which crystallise in the monoclinic C2/c space group, of which 32 are superconductors [1,2,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30]. The counter cation (A = H3O+/K+/NH4+/Rb+) and the tris(oxalato)metallate metal centre can be changed (M = Fe [1,7,8,9,10,11,12,13,14,15,16,17,18,19,25], Cr [20,21,22,23,24,25], Co [25], Al [25], Mn [17,26], Ga [24,27,28] Ru [29], Rh [30]), which has a small effect on the electrical properties of the material owing to the change in size of A and M. For example, β″-(BEDT-TTF)4(A)M(C2O4)3·G, where G = benzonitrile, sees a reduction of superconducting Tc to 5.5–6.0 K when M = Cr, compared to when M = Fe 7.0–8.5 K. A more marked effect on the electrical properties and the superconducting Tc [31] is observed when changing the guest molecule, G—the solvent used for the electrocrystallization. Changing G from benzonitrile to different sized and shaped guest molecules can alter the conducting properties from superconducting to metallic or semiconducting [2,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30]. The highest superconducting Tc values are obtained when longer guest solvent molecules are used, which increase the b axis length the furthest, e.g., G = benzonitrile, nitrobenzene [31].
When G = benzonitrile, crystals of an additional 4:1 orthorhombic phase are also obtained when M = Fe or Cr. Crystals of this 4:1 orthorhombic phase are the only phase obtained with G = benzonitrile when M = Co [25], Al [25], or Rh [30], and the β″ phase has not been reported. This semiconducting phase crystallises in the orthorhombic space group Pbcn with a pseudo-κ donor packing. (BEDT-TTF+)2 dimers are surrounded by neutral BEDT-TTF0 monomers. The –C≡N group of benzonitrile is disordered over two positions directed towards A, rather than along the b axis towards M, as seen in the β″ salts. The chirality of the tris(oxalato)metallates in the anion layers differs between the β″ and pseudo-κ salts despite both having an overall racemic lattice. In the β″ salts, each anion layer contains only a single enantiomer of M(C2O4)33− with alternating layers being of the opposing enantiomer. However, in the pseudo-κ salts, each anion layer is identical with alternating rows of Δ or Λ enantiomers.
When G is too large to fit inside the honeycomb cavity of the anion layer, a 4:1 triclinic phase is obtained. The guest molecule in these salts protrudes on one side of the anion layer and not on the other. The two different faces of the anion layer then lead to two different packing modes of the donor layer within the same crystal, e.g., both α and β″ donor packing (G = PhCH2CN, PhN(CH3)CHO, PhCOCH3, or PhCH(OH)CH3) [32] or α and pseudo-κ (G =1,2-Br2Ph) [33]. An α-β″ salt has also been obtained with the inclusion of a chiral guest molecule (G = sec-phenethyl alcohol, PhCH(OH)CH3) in both the chiral S form and the racemic R/S form. A small difference in the metal–insulator transition temperature is observed between the racemic and the chiral salts owing to the disorder, which is found only in the racemate [34].
While the 4:1 salts make up the majority of BEDT-TTF-tris(oxalate)metallate salts, some semiconducting 3:1 salts have been obtained when using smaller guest molecules (G = DMF, acetonitrile, dichloromethane, nitromethane; cation = Li+, Na+, NH4+; metal = Fe [35], Cr [36,37,38,39], Al [39]). A 2:1 salt has also been reported in which an 18-crown-6 molecule is the guest in the honeycomb cavity, β″-(BEDT-TTF)2[(H2O)(NH4)2M(C2O4)3].18-crown-6 (M = Cr, Rh, Ru, Ir). Both the Cr and Rh salts show a bulk Berezinskii–Kosterlitz–Thouless superconducting transition [40,41,42]. Changing the counter cation A has produced several salts where the packing of the anion layer differs from the aforementioned honeycomb packing arrangement giving salts β’-(BEDT-TTF)5[Fe(C2O4)3]·(H2O)2·CH2Cl2 [43] (A = tetraethylammonium), η-(BEDT-TTF)4(H2O)LiFe(C2O4)3 [35] (A = lithium), α‴-(BEDT-TTF)9[Fe(C2O4)3]8Na18(H2O)24 [44,45] (A = sodium, α-(BEDT-TTF)10(18-crown-6)6K6[Fe(C2O4)3]4(H2O)24 [45] (A = potassium), and α-(BEDT-TTF)12[Fe(C2O4)3]2·(H2O)n [46] (A = potassium or caesium, n = 15 or 16). Changing the M(III) to Ge(IV) produces very different structures in the semiconductors (BEDT-TTF)2[Ge(C2O4)3]∙PhCN [47], (BEDT-TTF)5[Ge(C2O4)3]2 [48], (BEDT-TTF)7[Ge(C2O4)3]2(CH2Cl2)0.87(H2O)0.09 [48], and (BEDT-TTF)4Ge(C2O4)3·(CH2Cl2)0.50 [49].
We report here the synthesis, crystal structures, and conducting properties of the first superconductor incorporating the tris(oxalato)aluminate anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br (Tc ~ 2.5 K), the first example of a β″ phase for the tris(oxalato)cobaltate anion (G = PhBr), and two new β″ salts from tris(oxalato)ruthenate (G = PhCl or PhF). Resistivity is also presented for β″-(BEDT-TTF)4(H3O)Ru(C2O4)3.PhBr, which shows a superconducting Tc of 2.8 K, though the crystals were very thin and not suitable for a publishable X-ray dataset.

2. Results and Discussion

All salts β″-(BEDT-TTF)4(H3O)M(C2O4)3·G (M-G = Al-PhBr, Co-PhBr, Ru-PhCl, Ru-PhF) are isostructural with the previously reported Day series β″-(BEDT-TTF)4[(A)M(C2O4)3]·G. Ru-PhBr is also isostructural, though the crystals were very thin and not suitable for a publishable X-ray dataset. They crystallise in the monoclinic space group C2/c. The asymmetric unit contains two crystallographically independent BEDT-TTF molecules, half an M(C2O4)3− molecule, half a guest halobenzene molecule, and half a H3O+ molecule (Table 1). The long-range structure consists of ordered alternating layers of BEDT-TTF donor molecules and M(C2O4)3− anions (Figure 1). The two crystallographically independent donor BEDT-TTF molecules form two-dimensional stacks along the a/b crystallographic axis in a β″ arrangement (Figure 2). A number of predominately side-to-side sulphur-sulphur interactions below the sum of the van der Waals radii are present (Table 2). The estimated charge on BEDT-TTF cations can be calculated via the method of Guionneau et al. [50] from the central C=C and C–S bond lengths of the TTF core and results in a charge of approximately +0.5 for each BEDT-TTF molecule, as expected (Table 3).
The anion layer consists of a honeycomb arrangement of M(C2O4)3−, perpendicular to the long axis of the BEDT-TTF molecules, resulting in a hexagonal cavity that is occupied by the guest halobenzene molecule. Each anion layer contains a single enantiomer of the tris(oxalato)metallate ion with adjacent layers containing the alternate enantiomer, which gives an overall racemic lattice. The hexagonal cavity and the orientation of the guest halobenzene molecule within it are shown in Figure 3 and Table 4. Distances a, b, h, and w represent the dimensions of the hexagonal cavity. The latter two are the height and width of the cavity, respectively, and δ is the angle of the benzene ring plane relative to the plane of the hexagonal cavity (measured as the least-squares plane of the three metal atoms making up three corners of the hexagon). For M = Rh, we see a reduction in height (h) of the hexagonal cavity going from G = PhCl to the smaller PhF, accompanied by a reduction in the length of the b axis of the unit cell. For salt Al-PhBr, we observed a Tc of ~2.5 K (Figure 4), which is similar to previously published salts of β″-(BEDT-TTF)4[(H3O)M(C2O4)3].G, where G = bromobenzene. When applying a magnetic field along the c* axis, the critical field of the superconductivity at 0.7 K is about 0.2 T. This is comparable to other salts in the Day series, for example: the Fe-DMF salt has a Tc of 2.0 K, and Hc2 in a perpendicular field is ~0.1 T [51]. Higher Tc salts in the Day series have higher Hc2 values (2–5 T) [52], and these quasi-2D superconductors are strongly anisotropic [53].
The Al3+ ion of tris(oxalato)aluminate is smaller than previous examples, where M = Fe [13,17], Ga [28], Rh [30], and Ru [29] (Tc = ~3.8, ~3.0, ~2.9, ~2.8 K, respectively, for G = bromobenzene), and the Tc is smaller for M = Al at ~2.5 K. A comparison of the b axis length of these bromobenzene salts at room temperature showed that the M = Fe salt has the longest at 20.0546(15) Å and also the highest ~3.8 K [13,17]; M = Rh has an intermediate b axis of 20.0458(4) Å and a Tc of ~2.9 K [30]; while M = Al has the shortest b axis of 19.9472(4) Å and the lowest Tc at ~2.5 K. A direct comparison with the M = Ga [28] and Ru [29] salts cannot be made owing to A = Kx(H3O)1-x rather than H3O for these salts. Salts with M = Cr [23] and Mn [17] have been reported with Tcs of 1.5 K and 2.0 K, respectively, but crystal structures are not published for the comparison of the b axes. Our crystals of Co-PhBr did not show superconductivity (Figure 5), with the b axis of this salt being much shorter than all other PhBr salts at 19.7508(5) Å.
There are thirty-two superconductors to date having the formula β″-(BEDT-TTF)4[(A)M(C2O4)3]·G (M = Fe, Cr, Ga, Rh, Ru, Mn, G = guest molecule, A = H3O+/K+/NH4+) [1,2,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30]. There is negligible π-d interaction in β″-(BEDT-TTF)4[(A)M(C2O4)3]. G salts because the M3+ ions are located in the centre of the anion layer, distant from the BEDT-TTF layer (Figure 1). This is confirmed by the similar Tcs that are observed for isostructural salts with the same A and G, but which differ only in the presence of paramagnetic Fe3+ (S = 5/2) or non-magnetic Ga3+ [53,54]. A much more marked effect on the value of Tc is observed when changing the guest molecule, G. Changing M and G leads to a change in the length of the unit cell dimensions. A correlation between the b axis length and superconducting Tc has been observed through structural analysis [31]. The effect of chemical pressure through changing G and M is mainly attributed to the guest molecule, G, which is oriented with the R-group oriented in the b direction (Figure 3). The longest molecules, benzonitrile and nitrobenzene, have the highest Tcs observed in the family, and the relationship between Tc and the guest molecule size can be observed in the series of salts with halobenzene guest molecules [31]. Only the higher Tc salts in this family show insulating behaviour just above Tc owing to charge disproportionation in these salts [55,56,57,58].
Figure 6 shows the resistivity of β″-(BEDT-TTF)4(H3O)Ru(C2O4)3·G, where G = PhBr, PhCl, or PhF. Ru-PhBr for A = Kx(H3O)1-x has previously been studied by Prokhorova et al. [29] with a sample-dependent Tc in the range 2.8–6.3 K. Resistivity measurements on our crystals of β″-(BEDT-TTF)4(H3O)Ru(C2O4)3.PhBr gave a Tc of 2.8 K, which was as expected based on the b axis length [31]. Upon reducing the size of G from PhBr to PhCl or PhF, no superconductivity was observed. Both Ru-PhCl and Ru-PhF showed semiconducting behaviour (Figure 6). Both Ru-PhCl and Ru-PhF had shorter b axis lengths compared to the Ru-PhBr salt. However, the b axis lengths in semiconducting Ru-PhCl and Ru-PhF were longer than that in superconducting Al-PhBr (Table 3). This indicates that other factors, such as the shape and the electric dipole of the guest molecule, may have minor influences even though the b axis length predominantly affects the electronic state, including the Tc [31].

3. Materials and Methods

Bromobenzene, chlorobenzene, fluorobenzene, ethanol, and 18-crown-6 were purchased from Sigma Aldrich and used as received. BEDT-TTF was purchased from Sigma Aldrich (Gillingham, Dorset, UK) and recrystallised from chloroform.

3.1. Synthesis

Ammonium tris(oxalato)aluminate and tri(oxalato)cobaltate were synthesised by the method of Bailar and Jones [59]. Ammonium tris(oxalato)ruthenate was synthesised by the method of Kaziro et al [60].
Al-PhBr: One-hundred milligrams of ammonium tris(oxalato)aluminate and 200 mg of 18-crown-6 ether were dissolved in 10 mL 1,2,4-trichlorobenzene, 10 mL bromobenzene, and 2 mL ethanol. The solution was then filtered into the cathodic side of the H-cell, while 20 mg of BEDT-TTF was added to the anodic side of the H-cell. The level of solvent was allowed to equilibrate in the cell, and a platinum electrode was added to each side. A constant current of 0.8 µA was applied across the H-cell which gave small black crystals of Al-PhBr which were collected after 28 days.
Co-PhBr: One-hundred milligrams of ammonium tris(oxalato)cobaltate and 200 mg of 18-crown-6 ether were dissolved in 10 mL 1,2,4-trichlorobenzene, 10 mL bromobenzene, and 2 mL ethanol. Ten milligrams of BEDT-TTF were added to the anodic side of the H-cell. A constant current of 0.6 µA was applied across the H-cell which gave tiny black crystals of Co-PhBr which were collected after 14 days.
Ru-PhF: One-hundred milligrams of ammonium tris(oxalato)ruthenate and 200 mg of 18-crown-6 ether were dissolved in 10 mL 1,2,4-trichlorobenzene, 10 mL fluorobenzene, and 2 mL ethanol. Ten milligrams of BEDT-TTF were added to the anodic side of the H-cell. A constant current of 1.0 µA was applied across the H-cell which gave black block crystals of Ru-PhF which were collected after 28 days.
Ru-PhCl: One-hundred milligrams of ammonium tris(oxalato)ruthenate and 200 mg of 18-crown-6 ether were dissolved in 10 mL 1,2,4-trichlorobenzene, 10 mL chlorobenzene, and 2 mL ethanol. Ten milligrams of BEDT-TTF were added to the anodic side of the H-cell. A constant current of 1.0 µA was applied across the H-cell which gave black block crystals of Ru-PhCl which were collected after 28 days.
Ru-PhBr: One-hundred milligrams of ammonium tris(oxalato)ruthenate and 200 mg of 18-crown-6 ether were dissolved in 10 mL 1,2,4-trichlorobenzene, 10 mL chlorobenzene, and 2 mL ethanol. Ten milligrams of BEDT-TTF were added to the anodic side of the H-cell. A constant current of 1.0 µA was applied across the H-cell which gave thin needle crystals of Ru-PhBr which were collected after 28 days. The crystals were very thin and not suitable for a publishable X-ray dataset.

3.2. Single-Crystal X-ray Crystallography

Data were collected using a RigakuRapid II (Tokyo, Japan) imaging plate system with the MicroMax-007 HF/VariMax rotating-anode X-ray generator and confocal monochromated Mo-Kα radiation.

3.3. Conducting Properties

Out-of-plane electrical resistance was measured using the standard four-terminal AC method with the current along the c* axis. Four gold wires were attached using carbon paint on both plane surfaces of single crystals.

4. Conclusions

We reported the synthesis and characterization of β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br (Al-PhBr), which represents the first superconductor in the Day series to contain the tris(oxalato)aluminate anion. This salt (M = Al) is isostructural with bromobenzene salts where M = Fe, Ga, Rh, Ru, Mn, Cr. A relationship between the b axis length and superconducting Tc has previously been observed in the Day series [31]. The b axis length of these bromobenzene salts at room temperature showed that the M = Fe salt had the longest b axis and also the highest Tc of ~3.8 K, while M = Al had the shortest b axis and the lowest Tc of ~2.5 K. We also reported the isostructural M = Co salt (Co-PhBr), which did not show superconductivity. The b axis of this salt was much shorter than all other bromobenzene salts. Isostructural salts Ru-PhCl and Ru-PhF were presented in which the b axes were longer than that observed in superconducting Al-PhBr, but these two ruthenium salts did not show superconductivity. This indicates that even though the b axis length predominantly affected the electronic state, including the Tc, other factors may also be at work, such as the shape and the electric dipole of the guest molecules, which may have minor influences on the electronic states.

Author Contributions

Synthesis, L.M., M.B. and J.M.-N.; X-ray crystallography, T.J.B., H.A. and Y.N.; conductivity measurements S.I., H.A. and Y.N.; writing—original draft preparation, L.M. and T.J.B.; project administration, L.M.; funding acquisition, L.M. All authors have read and agreed to the published version of the manuscript.

Funding

L.M. and T.J.B. would like to thank The Leverhulme Trust for financial support (RPG-2019-242).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

CCDC 2084688-2084692 contains supplementary X-ray crystallographic data for Al-PhBr (100 K), Al-PhBr (298 K), Co-PhBr, Ru-PhCl, and Ru-PhF, respectively. https://www.ccdc.cam.ac.uk/structures/.

Acknowledgments

This article is dedicated to Peter Day, who was an inspirational chemist and a dear friend to those authors of this paper who had the pleasure of working with him.

Conflicts of Interest

The authors declare no conflict of interest.

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Magnetochemistry 07 00090 g001 550
Figure 1. Layered structure of Al-PhBr. The other salts reported in this paper are isostructural. Carbon atoms are grey, hydrogen atoms white, oxygen atoms red, sulphur atoms yellow, aluminium atoms pink, and bromine atoms brown. The b axis is shown in green, and the c axis is shown in blue.
Figure 1. Layered structure of Al-PhBr. The other salts reported in this paper are isostructural. Carbon atoms are grey, hydrogen atoms white, oxygen atoms red, sulphur atoms yellow, aluminium atoms pink, and bromine atoms brown. The b axis is shown in green, and the c axis is shown in blue.
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Figure 2. β″ BEDT-TTF layer packing in Al-PhBr. The other salts reported in this paper are isostructural. The two crystallographically independent BEDT-TTF molecules are shown in different colours. Hydrogens have been removed for clarity. The a axis is shown in red, the b axis in green, and the c axis in blue.
Figure 2. β″ BEDT-TTF layer packing in Al-PhBr. The other salts reported in this paper are isostructural. The two crystallographically independent BEDT-TTF molecules are shown in different colours. Hydrogens have been removed for clarity. The a axis is shown in red, the b axis in green, and the c axis in blue.
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Figure 3. Honeycomb cavity in the anion layer of β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts with measurement parameters labelled (a–e, w = width, h = height). Carbon atoms are grey, hydrogen atoms white, and oxygen atoms red. This image shows salt Al-PhBr, where aluminium atoms are pink and bromine atoms brown.
Figure 3. Honeycomb cavity in the anion layer of β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts with measurement parameters labelled (a–e, w = width, h = height). Carbon atoms are grey, hydrogen atoms white, and oxygen atoms red. This image shows salt Al-PhBr, where aluminium atoms are pink and bromine atoms brown.
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Figure 4. Electrical resistivity for Al-PhBr.
Figure 4. Electrical resistivity for Al-PhBr.
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Figure 5. Electrical resistivity for Co-PhBr.
Figure 5. Electrical resistivity for Co-PhBr.
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Figure 6. Electrical resistivity for β″-(BEDT-TTF)4(H3O)Ru(C2O4)3·G where G = PhBr, PhCl, or PhF.
Figure 6. Electrical resistivity for β″-(BEDT-TTF)4(H3O)Ru(C2O4)3·G where G = PhBr, PhCl, or PhF.
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Table
Table 1. Crystal data for β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts.
Table 1. Crystal data for β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts.
SaltAl-PhBr 290 KAl-PhBr 110 KCo-PhBr 150 KRu-PhF 293 KRu-PhCl 298 K
FormulaC52H40AlBrO13S32C52H40AlBrO13S32C52H40BrCoO13S32C52H40FO13RuS32C52H40O13S32ClRu
Fw (g mol−1)2005.652005.652037.602018.832035.28
Crystal Systemmonoclinicmonoclinicmonoclinicmonoclinicmonoclinic
Space groupC2/cC2/cC2/cC2/cC2/c
Z44444
T (K)290 (2)110 (2)150 (2)293 (2)293 (2)
a  ( Å ) 10.2851 (2)10.2520 (3)10.2306 (3)10.32786 (19)10.32017 (19)
b   ( Å ) 19.9472 (4)19.7919 (7)19.7508 (5)19.9521 (4)20.0264 (4)
c   ( Å ) 35.597 (3)35.4275 (11)35.2520 (9)34.9966 (6)35.161 (3)
α   ( ° ) 9090909090
β   ( ° ) 93.399 (7)93.843 (7)93.938 (7)93.010 (7)93.586 (7)
γ   ( ° ) 9090909090
Volume ( Å 3 ) 7290.1 (6)7172.3 (4)7106.3 (3)7201.5 (2)7252.6 (6)
Density (g cm−3)1.8271.8571.9051.8621.864
μ (mm−1)1.5531.5781.8061.2091.235
R 1 0.05470.06880.04310.04600.0442
w R   ( a l l   d a t a ) 0.14010.15260.09140.3180.1089
Table
Table 2. S…S close contacts below the van der Waals distance in β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts.
Table 2. S…S close contacts below the van der Waals distance in β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts.
Contact (Å)Al-PhBr 290 KAl-PhBr 110 KCo-PhBr 150 KRu-PhF 293 KRu-PhCl 298 K
S1…S73.4069 (13)3.3795 (19)3.3683 (11)3.4015 (14)3.4283 (11)
S3…S73.5046 (13)3.458 (2)3.4544 (11)3.5369 (15)3.5290 (11)
S2…S93.3138 (14)3.2838 (19)3.2864 (11)3.3744 (15)3.3528 (11)
S2…S113.3720 (13)3.340 (2)3.3413 (11)3.3954 (15)3.3842 (11)
S6…S153.5231 (14)3.463 (2)3.4475 (12)3.5236 (17)3.5190 (13)
S8…S153.5704 (15)3.502 (2)3.4904 (13)3.6182 (17)3.5869 (12)
S8…S103.5889 (14)3.550 (2)3.5551 (13)3.6169 (16)3.6031 (13)
Table
Table 3. Average bond lengths (Å) in BEDT-TTF molecules with approximation of the charge on the molecules. δ = (b + c) − (a + d), Q = 6.347 − 7.463δ [50].
Table 3. Average bond lengths (Å) in BEDT-TTF molecules with approximation of the charge on the molecules. δ = (b + c) − (a + d), Q = 6.347 − 7.463δ [50].
Magnetochemistry 07 00090 i001
SaltDonorabcdδQ
Al-PhBr 290 KA1.3761.739251.75151.3520.7630.65
B1.3731.740251.7531.3470.7730.58
Al-PhBr 110 KA1.3641.744751.756751.3460.7920.44
B1.3761.74351.757251.34550.7790.53
Co-PhBr 150 KA1.3671.737751.752751.3450.7790.54
B1.3691.7381.75151.3460.7750.57
Ru-PhF 293 KA1.361.73851.744751.3490.7740.57
B1.3671.733251.745251.3540.7580.69
Ru-PhCl 298 KA1.3661.7371.74751.3490.7700.60
B1.3661.735751.746251.3490.7670.62
Table
Table 4. Honeycomb cavity measurements in the anion layer (see Figure 3) of β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts.
Table 4. Honeycomb cavity measurements in the anion layer (see Figure 3) of β″-(BEDT-TTF)4(H3O)M(C2O4)3·G salts.
Salt Temp.Al-PhBr 290 KAl-PhBr 110 KCo-PhBr 150 KRu-PhF 293 KRu-PhCl 298 K
Distances (Å)
a6.269 (3)6.255 (6)6.249 (3)6.292 (3)6.312 (2)
b6.387 (5)6.111 (10)6.286 (6)6.380 (5)6.377 (4)
c4.5360 (16)4.487 (3)4.5212 (10)4.804 (13)4.331 (16)
d1.894 (6)1.905 (10)1.902 (6)1.377 (14)1.737 (6)
e4.401 (9)4.338 (19)4.296 (10)4.786 (13)4.543 (9)
h13.560 (5)13.481 (10)13.464 (6)13.572 (5)13.649 (4)
w10.2851 (2)10.2520 (3)10.2306 (3)10.32786 (19)10.32017 (19)
O4-cation3.066 (5)3.004 (11)2.985 (6)2.956 (6)2.962 (5)
O6-cation2.857 (3)2.851 (6)2.842 (3)2.846 (6)2.831 (3)
O1-cation3.083 (5)3.073 (9)3.112 (5)2.941 (5)2.996 (4)
Angles (°)
δ 33.522 (3)33.378 (3)33.60 (13)33.74 (19)32.677 (3)
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Blundell, T.J.; Brannan, M.; Mburu-Newman, J.; Akutsu, H.; Nakazawa, Y.; Imajo, S.; Martin, L. First Molecular Superconductor with the Tris(Oxalato)Aluminate Anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, and Isostructural Tris(Oxalato)Cobaltate and Tris(Oxalato)Ruthenate Radical Cation Salts. Magnetochemistry 2021, 7, 90. https://doi.org/10.3390/magnetochemistry7070090

AMA Style

Blundell TJ, Brannan M, Mburu-Newman J, Akutsu H, Nakazawa Y, Imajo S, Martin L. First Molecular Superconductor with the Tris(Oxalato)Aluminate Anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, and Isostructural Tris(Oxalato)Cobaltate and Tris(Oxalato)Ruthenate Radical Cation Salts. Magnetochemistry. 2021; 7(7):90. https://doi.org/10.3390/magnetochemistry7070090

Chicago/Turabian Style

Blundell, Toby James, Michael Brannan, Joey Mburu-Newman, Hiroki Akutsu, Yasuhiro Nakazawa, Shusaku Imajo, and Lee Martin. 2021. "First Molecular Superconductor with the Tris(Oxalato)Aluminate Anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, and Isostructural Tris(Oxalato)Cobaltate and Tris(Oxalato)Ruthenate Radical Cation Salts" Magnetochemistry 7, no. 7: 90. https://doi.org/10.3390/magnetochemistry7070090

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