Table 2 Energy gaps between the occupied 4 s/5 s- and unoccupied 4p/5p-orbitals as well as singlet-triplet gaps of [M(C6H5F)2]+, [M(bipy)]+ and [M(bipy)2]+ in kJ mol−1 (M=Ga, In; gas phase, 298.15 K, 1.0 bar, values at BHLYP/SV(P)/B3LYP/SV(P) level).

From: Cationic cluster formation versus disproportionation of low-valent indium and gallium complexes of 2,2’-bipyridine

 

Δ E (kJ mol−1) (M=Ga)

Δ E [kJ mol−1] (M=In)

 

4 s/4p

singlet-triplet

5 s/5p

singlet-triplet

[M(C6H5F)2]+

853/653

311/-*

797/618

-*/-†

[M(bipy)]+

582/386

196/-†

580/383

227/-†

[M(bipy)2]+

709/507

5‡/21‡

645/471

111§/96§

  1. *Even after 500 iteration cycles, the geometry optimization of the triplet state did not converge.
  2. †Though the geometry optimization converged, the electronic occupation of the triplet state is not correctly described.
  3. ‡The significant decrease of ΔE is accompanied by a geometry change of the [Ga(bipy)2]+ complex from a tetragonal pyramidal to a tetrahedral coordination mode in the singlet and triplet state, respectively (Supplementary Table 12).
  4. §The [In(bipy)2]+ complex features a tetragonal pyramidal coordination mode both in the singlet and the triplet state (Supplementary Table 12).
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