SUPPLEMENTARY MATERIAL:

Table S1 Crystal data and structure refinement for 1 and 2.

1 / 2
Empirical formula / C66H98Cl5Fe3LiO9 / C66H98Cl2CrLiO9
Formula weight / 1387.18 / 1165.28
Temperature / 200(2) K / 200(2) K
Wavelength / 0.71073 Å / 0.71073 Å
Crystal system / Monoclinic / Triclinic
Space group / P21/n / P-1
Unit cell dimensions / a = 13.6658(10) Å / a = 11.6687(8) Å.
b = 33.2180(16) Å / b = 14.4323(11) Å.
c = 15.7214(9) Å / c = 20.6793(14) Å.
α = 91.255(6)°.
β = 102.059(5)°. / β = 100.492(5)°.
γ = 107.899(5)°.
Volume / 6979.3(7) Å3 / 3247.3(4) Å3
Z / 4 / 2
Density (calculated) / 1.320 Mg/m3 / 1.192 Mg/m3
Absorption coefficient / 0.858 mm-1 / 0.311 mm-1
F(000) / 2928 / 1254
Theta range for data collection / 1.80 to 29.20°. / 1.49 to 25.00°.
Index ranges / -13<=h<=18
-34<=k<=44
-21<=l<=21 / -13<=h<=13
-17<=k<=17
-24<=l<=24
Reflections collected / 40668 / 60965
Independent reflections / 17460 [R(int) = 0.0666] / 11345 [R(int) = 0.1307]
Completeness to theta = 25.00° / 96.7 % / 99.1 %
Absorption correction / None / Empirical (SHELXA)
Refinement method / Full-matrix least-squares on F2 / Full-matrix least-squares on F2
Data / restraints / parameters / 17460 / 0 / 771 / 11345 / 0 / 546
Goodness-of-fit on F2 / 0.992 / 0.739
Final R indices [I>2sigma(I)] / R1 = 0.0526, wR2 = 0.1427 / R1 = 0.0549, wR2 = 0.1141
R indices (all data) / R1 = 0.0995, wR2 = 0.1909 / R1 = 0.1202, wR2 = 0.1324
Largest diff. peak and hole / 0.985 and -0.868 e.Å-3 / 0.366 and -0.238 e.Å-3

Figure S1: Scheme of lithiated p-tert-butylcalix[4]arene;(left) crystallization under argon; (right) crystallization in air; Some H atoms and free THF molecules are omitted for clarity; one on the free THF molecule is placed in the cavity.[46]

Figure S2: molecular view of 1; H atoms are omitted for clarity.

Figure S3: molecular view of 2; H atoms and THF solvate molecules are omitted for clarity.

In the unit cell, the molecules are arranged in line with the organisation “ABAB”, where B can be also described as “–A”. Indeed line “A” and line “B” are oriented in opposite directions (figure 4). Free space in the unit cell is filled with eight free THF molecules (four molecules per calixarene).

Figure S4: Molecular packing of 2; H atoms are omitted for clarity.

Figure S5: Graphical representation of angles between the opposite central carbon atom of the tert-butyl group for different calixarene structures; left bars represent angles between plan containing methoxy-substituted rings; the right bars the angles between hydroxy-substituted rings. With Empty,[73] Toluene,[74] Acetonitrile,[75] Acetonitrile, [75], R,[23] Half-lithiated (THF),[46] Fully lithiated.(Li-THF) [46]

Bond Angle Variance and Quadratic Elongation.

Robinson and Gibbs introduced in 1971 two parameters: [S1] bond angle variance (σ2) and mean quadratic elongation (λ). For a distorted octahedron MX6 angle variance and quadratic elongation are defined to be:

σoct2=111i=112(θi-90)2 ; λoct=16i=16(li-l0)2

Where θi are the X-M-X angles in the distorted octahedron, li is the length of the bond from the central M atom to the ith X atom in the octahedron and l0 is the bond length for the ideal, regular octahedron equal in volume to the one in question. Similar parameters are available for the tetrahedron:

σtet2=15i=16(θi-109.47)2 ; λtet=14i=14(li-l0)2

These parameters are calculated with PLATON software.[55]

In the cationic unit of compound 1, Li1 is linked to four THF-O-atoms O6-O9 with bond lengths from 1.927(7) Å for O7 to 1.964(7) Å for O9. The tetrahedral volume of the lithium coordination architecture is 3.704 Å3 (QE 1.006, AV 20.46°2), which is extremely close from the perfect tetrahedral coordination.[S2] For the tetrahedrally coordinated Fe2 and Fe3, the tetrahedral volume (TV) is equal to 5.447 Å3, with a quadratic elongation (QE) λ of 1.047 and an angle variance (AV) σ2 of 150.60 °2, respectively a volume of 4.900 Å (QE λ = 1.038, AV: σ2 = 97.82 °2). For compound 2, these parameters are 12.017 Å3 for the octahedral volume, λ = 1.012 for the quadratic elongation and σ2 = 23.84°2 for the angle variance.

[S1] K. Robinson, G.V. Gibbs, P.H. Ribbe, Science 172 (1971) 567–570.

[S2] M.Å. Dahlborg, G. Svensson, P. Sartori, Acta Chem. Scand. 53 (1999) 1103–1109.