Table 2.

Experimental and calculated (gas‐phase) electrochemical properties of monomers 3  a–c, dimers 3  a₂ –c₂ and trimers 3  a_{3 ‐} c₃   in solution (CH₂Cl₂).

Compd	E (0/−) [V][a]	Ionization potential [ev] [b]	HOMO [eV][c]	Electron affinity [eV][d]	LUMO [eV][c]
3  a	−1.81	−5.92	−5.55	−3.29	−2.76
3  a2	–[e]	–[e]	−5.41	−[e]	−2.99
3  a3	−1.80	−5.78	−5.37	−3.30	−2.98
3  b	−1.31		−6.07	−3.79	−3.23
3  b2	–	–	−6.03	−	−3.52
3  b3	−1.38		−6.00	−3.72	−3.50
3  c	−1.11		−5.63	−3.99	−3.46
3  c2	−1.02	−5.93	−5.60	−4.08	−3.72
3  c3	−1.05	−5.87	−5.58	−4.05	−3.70

[a] First reduction potentials from cyclic voltammetry (CV) in CH₂Cl₂ at room temperature with Bu₄NPF₆ as the electrolyte against Fc/Fc⁺ as an internal standard (−5.10 eV) ^[14] at 0.2 or 0.5 V/s. [b] Ionization potential=electron affinity−λ _onset,abs. [c] Obtained from DFT calculations (Gaussian16,¹⁵B3LYP/def2‐TZVP). [d] Electron affinity=−e×(5.1 V+E ^(0/−)). [e] Measurement not possible due to insufficient solubility.