LAUSR

Abstract Multinuclear transition metal complexes bridged by ligands with extended π‐electronic systems show a variety of complex electronic transitions and electron transfer reactions. While a systematic understanding of the photochemistry and electrochemistry has been attained for binuclear complexes, much less is known about trinuclear complexes such as hexaphenyl‐5,6,11,12,17,18‐hexaazatrinaphthylene‐tristitanocene [(Cp2Ti)3HATN(Ph)6]. The voltammogram of [(Cp2Ti)3HATN(Ph)6] shows six oxidation and three reduction waves. Solution spectra of [(Cp2Ti)3HATN(Ph)6] and of the electrochemically formed oxidation products show electronic transitions in the UV, visible and the NIR ranges. Density functional theory (DFT) and linear response time‐dependent DFT show that the three formally titanium(II) centers transfer an electron to the HATN ligand in the ground state. The optically excited transitions occur exclusively between ligand‐centered orbitals. The charged titanium centers only provide an electrostatic frame to the extended π‐electronic system. Complete active self‐consistent field (CASSCF) calculation on a structurally simplified model compound, which considers the multi‐reference character imposed by the three titanium centers, can provide an interpretation of the experimentally observed temperature‐dependent magnetic behavior of the different redox states of the title compound in full consistency with the interpretation of the electronic spectra.