Supporting Information

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1 Supporting Information U h (7)-C 80 :Crystallographic characterization of a long-sought dimetallic actinide endohedral fullerenes Xingxing Zhang, a Yaofeng Wang, a Roser Morales-Martínez, b Jun Zhong, e Coen de Graaf, b,f Antonio Rodríguez-Fortea, b Josep M. Poblet,* b Luis Echegoyen,* c Lai Feng* d and Ning Chen* a [a] Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, , (P.R. China). chenning@suda.edu.cn [b] Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, c/marcel lí Domingo 1, Tarragona, (Spain) josepmaria.poblet@urv.cat [c] Department of Chemistry, University of Texas at El Paso, 500 W University Avenue, El Paso, Texas (United States) echegoyen@utep.edu [d] Soochow Institute for Energy and Materials InnovationS (SIEMIS), College of Physics, Optoelectronics and Energy & Collaborative, Soochow University, Suzhou, Jiangsu, (P. R. China) fenglai@suda.edu.cn [e] Jiangsu Key Laboratory for Carbon-based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou, Jiangsu, , (P.R. China). jzhong@suda.edu.cn [f] ICREA, Pg Lluis Companys 23, Barcelona 08010, Spain S1

2 Table of Contents Figure S1. MALDI-TOF mass spectrum of the as-extracted solution of the fullerene mixture... S3 Figure S2. Separation of U h (7)-C S3 Figure S3. X-ray structures S i -S iv.... S4 X-ray studies.... S4 Table S1. U-U distancesa (Å) in X-ray model.... S4 Table S2. U-C distances in X-ray model of S i.... S5 Table S3. U-C distances in X-ray model of S ii.... S5 Table S4. U-C distances in X-ray model of S iii.... S6 Table S5. U-C distances in X-ray model of S iv.... S6 Figure S4. Differential pulse voltammogram of U h (7)-C S6 Table S6. Relative energies, computed U-U and U-C and spin densities for the four U h (7)-C 80 structures S i -S iv.... S7 Table S7. Relative energies, computed U-U distances and spin densities for the five U h (7)-C 80 structures S v -S ix.... S7 Table S8. Optimized U-U distances and selected bonding parameters for S vi, S vii and S ix models.... S8 Figure S5. Representation of S v -S ix models once optimized.... S8 Figure S6. Spin density and plots of the electron localization function (ELF) on a plane containing the U 2 unit for the reduced, neutral and oxidized U h (7)-C 80 structure S iii.... S9 Figure S7. Computed Raman spectra for U h (7)-C 80 structures S i and S iii..... S9 S2

3 82 C 122 U@C 102 C 118 C 120 U@C 100 U@C 98 U 80 U 78 U 82 C 84 U@C m/z C 96 U@C 86 C116 C 124 C 92 C m/z Figure S1. Positive-ion mode MALDI-TOF mass spectrum of the as-extracted solution of the fullerene mixture. Figure S2. HPLC profiles showing the separation procedures of U h (7)-C 80 (left) and the corresponding MALDI-TOF mass spectra (right). S3

4 Figure S3. X-ray structures of S i -S iv X-ray studies. The cocrystal of U h -C 80 [Ni II (OEP)] CHCl 3 is monoclinic with a space group of C2/m. Thus, the asymmetric unit cell contains a half of the Ni II (OEP) molecule and a half of U h -C 80 molecule. The Ni II (OEP) molecule is fully ordered. As the symmetry plane of the I h -C 80 cage is not coincident with the crystallographic mirror plane, the intact I h -C 80 cage is formed by combining one of the halves of the carbon cage with the mirror image of the other. Thus, there are two orientations for I h (7)-C 80 cage, which occupy a common site with a common occupancy of 0.5. Inside the I h -C 80 cage, the endohedral U 2 cluster is highly disordered. Totally ten U sites can be identified, which can be classified as two groups (i.e., U1/U3/U5/U7/U9 and U2/U4/U6/U8/U10), each with the distribution over a belt-region near or opposite to the Ni II (OEP) moiety. All these disordered U sites were freely refined in the beginning and the U sites with similar occupancies were set into pairs in the final refinement. The sum of the occupancies of each group (i.e., U1/U3/U5/U7/U9 or U2/U4/U6/U8/U10) was adjusted to 0.5 in the final refinement. The occupancy of the U 2 set is ranging from 0.195(2) to (19). Table S1. U-U distances a (Å) in X-ray model. Occupancy U 2 set U-U distance (Å) U 2 set U-U distance (Å) 0.195(2) U1-U2=U1"-U2" 3.723(6) U1"-U2=U1-U2" 3.751(6) 0.124(2) U3-U4=U3"-U4" 3.793(7) U3"-U4=U3-U4" 3.390(9) b 0.083(2) U5-U6=U5"-U6" 3.653(12) U5"-U6=U5-U6" 3.100(16) b (19) U7-U8=U7-U8" 3.460(18) 0.055(4) U9-U (2) a As the symmetry plane of the I h -C 80 cage is not coincident with the crystallographic mirror plane, for each identified disordered U site, which is not residing on the crystallographic mirror plane (i.e., U1, U2, U3, U4, U5, U6, U8), another disordered U site with a common occupancy (i.e., U1", S4

5 U2", U3", U4", U5", U6", U8") can be generated via the crystallographic mirror plane. So, as listed in this table, for the U 2 set being off the mirror plane, two different U-U distances (i.e., U-U/U"-U" and U"-U/U-U") are possible crystallographically, though not both of them are acceptable from a chemical perspective. For the U 2 set with one or both U sites residing on the mirror plane, only one U-U distance is crystallographically available, so such a U-U distance can be unambiguously determined. b The computational optimizations starting from the X-ray models containing U3"-U4/U3-U4" or U5"-U6/U5-U6" revealed the optimized U-U distance is in a range of Å (see Table S6). So, the X-ray models containing U3"-U4/U3-U4" or U5"-U6/U5-U6" are considered to be unreasonable and discarded according to the computations. Table S2. U-C distances (Å) in X-ray model S i containing U1, U2 sites, as shown in Figure 2. U-C Distance (Å) U-C Distance (Å) U1-C22B 2.483(18) U2-C32B 2.375(16) U1-C23B 2.579(16) U2-C33B 2.339(17) U1-C24B 2.554(17) U2-C34B 2.45(2) U1-C43B 2.396(16) U2-C53B 2.495(19) U1-C44B 2.386(15) U2-C54B (17) U1-C45B 2.53(2) U2-C55B 2.552(16) Table S3. U-C distances (Å) in X-ray model S ii containing U1", U2" sites. U-C Distance(Å) U-C Distance(Å) U1-C22B 2.230(17) U2-C32B 2.546(16) U1-C23B 2.514(16) U2-C33B 2.277(16) U1-C24B 2.775(17) U2-C34B 2.26(2) U1-C43B 2.317(16) U2-C53B 2.752(19) U1-C44B 2.610(17) U2-C54B (17) U1-C45B 2.87(2) U2-C55B 2.498(16) S5

6 Table S4. U-C distances (Å) in X-ray model of S iii containing U1, U2" sites. U-C Distance(Å) U-C Distance(Å) U1-C22B 2.483(18) U2-C32B 2.546(16) U1-C23B 2.579(16) U2-C33B 2.277(16) U1-C24B 2.554(17) U2-C34B 2.26(2) U1-C43B 2.396(16) U2-C53B 2.752(19) U1-C44B 2.386(15) U2-C54B (17) U1-C45B 2.53(2) U2-C55B 2.498(16) Table S5. U-C distances (Å) in X-ray model of S iv containing U1", U2 sites. U-C Distance(Å) U-C Distance(Å) U1-C22B 2.230(17) U2-C32B 2.375(16) U1-C23B 2.514(16) U2-C33B 2.339(17) U1-C24B 2.775(17) U2-C34B 2.45(2) U1-C43B 2.317(16) U2-C53B 2.495(19) U1-C44B 2.610(17) U2-C54B (17) U1-C45B 2.87(2) U2-C55B 2.552(16) Current/A Figure S4. Differential pulse voltammogram of U h (7)-C 80 in o-dichlorobenzene (0.05 M(n-Bu) 4 NPF 6 ; scan rate 20 mvs Potential (V) vs Fc/Fc + S6

7 Table S6. Relative energies, computed U-U and U-C distances and spin densities for the four U h (7)-C 80 structures (S i to S iv ) with slightly different positions of the U ions. a) S i S ii S iii S iv E U-U U1-C U2-C spin U spin U a) Energies in kcal mol -1 and distances in Å. Table S7. Computed relative energies, optimized U-U distances and spin densities for the five S v to S ix U h (7)-C 80 structures, along with their X-ray U-U distances. Structure X-ray U-U (Å) opt U-U (Å) E (kcal mol -1 ) Spin U Spin U S v S vi S vii S viii S ix The initial geometries used for the geometry optimizations are those obtained from the X-ray structure. All the models with initial distances smaller than 3.50 Å (S v, S vi, S viii and S ix ) lead to optimized distances between 3.62 and 3.79 Å. Therefore, we can consider that these short U-U distances, specially and Å are very unlikely. S7

8 Table S8. Optimized U-U distances and selected bonding parameters for S iii, S v, S vi and S vii models of U h (7)-C 80. S iii S v S vi S vii d U-U a δ(u,u) b BO c ρ(bcp) d a Distances in Å. b delocalization index; c Mayer bond order; d electron density at bond critical point (in e Å 3 ). Figure S5. Representation of the optimized structures for the five S v to S ix U h (7)-C 80 structures. S8

9 Figure S6. Spin density (top) and plots of the electron localization function (ELF) on a plane containing the U 2 unit (bottom) for the reduced, neutral and oxidized U h (7)-C 80 structure S iii. Figure S7. Computed Raman spectra for U h (7)-C 80 structures S i and S iii. Representation of the active normal modes of vibration with lowest wavenumbers. S9