Aromatic character of planar boron-based clusters revisited by ring current calculations

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1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2016 Supplementary Information Aromatic character of planar boron-based clusters revisited by ring current calculations Hung Tan Pham, a,b Kie Zen Lim c, Remco W. A. Havenith c and Minh Tho Nguyen d,* a Computational Chemistry Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam b Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam c Theoretical Chemistry, Zernike Institute for Advanced Materials and Stratingh Institute for Chemistry, University of Groningen, NL-9747 AG Groningen, The Netherlands Netherlands and Ghent Quantum Chemistry Group, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), B-9000 Gent, Belgium d Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium. The file contains: Scheme 1. Geometries of the most stable B6 and B6 2- clusters Scheme 2. Shape of the delocalized π and σ MOs of B6. Scheme 3. Optimized geometries of the lowest-lying structures of B8, B8 2- and B9 -. Scheme 4. Optimized structures of the anions B10 2- and B11 -. Scheme 5. The optimized structure of B12 and B13 +. Scheme 6. Optimized structure of the elongated dianions B14 2- and B Scheme 7. Optimized structures of B6H5 + and Li7B5H5 + * minh.nguyen@chem.kuleuven.be

2 Figure S1. The possible transitions of B 3 + cluster. Figure S2. The total, π and σ ring current maps of B7 -, B8 0/2- and B9 - clusters. The ring current density was calculated using B3LYP/6-311G* method. Figure S3. Schematic orbital-energy level for the symmetry allowed virtual excitations in the B7- boron cluster. Rotationally (translationally) allowed excitation is shown as hollow (solid) arrow. Figure S4. Schematic orbital-energy level for the symmetry allowed virtual excitations in the B10 2- boron cluster. Rotationally (translationally) allowed excitation is shown as hollow (solid) arrow. Figure S5. The MOs have main contributon to π and σ ring current of B12. Figure S6. Schematic orbital-energy level for the symmetry allowed virtual excitations in the B16 2- boron cluster. Rotationally (translationally) allowed excitation is shown as hollow (solid) arrow. Figure S7. The ring current maps of MOs which has main contribution to π and σ ring current density of B19 - and B Figure S8. The ring current maps of MOs which has main contribution to π and σ ring current density of a) Li7B5H5 + and b) B@B5H5 + Figure S9. The ring current maps of M@B6H6q with M=Co, Fe and Mn; q=+1,0, -1. Figure S10. The current density of MOs of Fe@B6H6 Figure S11. The ring current maps of σ MOs (a) π-mos (b) for Fe@B7H7 Figure S12. The ring current maps of BnCm cluster which isolectronic with B10 2-

3 B6 (C 5v 1 A 1 ) B6 2- (D 2h 1 A g ) Scheme 1. Geometries of the most stable B 6 and B 6 2- clusters HOMO HOMO HOMO-1 σ-mos HOMO-3 π-mo Scheme 2. Shape of the delocalized π and σ MOs of B 6.

4 B8 ( 3 B 2 D 7h) B8 2- ( 1 A 1 D 7h) B9 - ( 1 A 1g D 8h ) Scheme 3. Optimized geometries of the lowest-lying structures of B 8, B 8 2- and B 9-. B10 2- (C 2v 1 A 1) B 11 - (C 2v 1 A 1) Scheme 4. Optimized structures of the anions B and B 11-.

5 B12 (C 3v 1 A 1 ) B13 + (C 3v 1 A 1 ) Scheme 5. The optimized structure of B 12 and B 13+. B14 2- (C 2v 1 A 1 ) B16 2- (D 2h 1 A g ) Scheme 6. Optimized structure of the elongated dianions B and B B6H5 + (D 5h 1 A 1 ) Li7B5H5 + (D 5h 1 A 1 ) Scheme 7. Optimized structures of B 6H 5+ and Li 7B 5H 5 +

6 -6.0 e e a 2 e Figure S1. The possible transitions of B 3 + cluster.

7 (π+σ) electrons π electrons σ electrons B7 - C2v B8 C2V B8 2- D7h B9 - D7h Figure S2. The total, π and σ ring current maps of B 7-, B 8 0/2- and B 9 - clusters. The ring current density was calculated using B3LYP/6-311G* method.

8 Figure S3. Schematic orbital-energy level for the symmetry allowed virtual excitations in the B7- boron cluster. Rotationally (translationally) allowed excitation is shown as hollow (solid) arrow.

9 Figure S4. Schematic orbital-energy level for the symmetry allowed virtual excitations in the B10 2- boron cluster. Rotationally (translationally) allowed excitation is shown as hollow (solid) arrow.

10 HOMO-HOMO HOMO-1,1 Figure S5. The MOs have main contributon to π and σ ring current of B 12.

11 Figure S6. Schematic orbital-energy level for the symmetry allowed virtual excitations in the B16 2- boron cluster. Rotationally (translationally) allowed excitation is shown as hollow (solid) arrow.

12 π-electrons σ-electrons π-electrons σ-electrons HOMO-1,1 HOMO-2,2 HOMO-1 HOMO-3 B 19 - B Figure S7. The ring current maps of MOs which has main contribution to π and σ ring current density of B 19 - and B

13 HOMO-HOMO HOMO-1 HOMO-2,2 HOMO-3,3 a) HOMO-HOMO HOMO-1 HOMO-2,2 b) Figure S8. The ring current maps of MOs which has main contribution to π and σ ring current density of a) Li 7B 5H 5 + and b) B@B 5H 5 +

14 Total σ-electrons π-electrons D 6h FeB 6H 6 D 6h FeB 6H 6 D 6h MnB 6H 6 - Figure S9. The ring current maps of M@B6H6q with M=Co, Fe and Mn; q=+1,0, -1.

15 HOMO HOMO-1 HOMO-2,2 HOMO-3 HOMO-4,4 HOMO-5,5 HOMO-6 HOMO-7,7 HOMO-8,8 HOMO-9 Figure S10. The current density of MOs of 6H 6

16 HOMO HOMO-2,2 HOMO-4,4 HOMO-5,5 HOMO-6,6 HOMO-7 a) HOMO-1 HOMO-3,3 Figure S11. The ring current maps of σ MOs (a) π-mos (b) for 7H 7 b) (σ+π) electrons π-electrons σ-electrons

17 CB9 - C2B8 C2B8 2- C3B7 - Figure S12. The ring current maps of B nc m cluster which isolectronic with B 10 2-

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