Electronic states of bis(phthalocyaninato)lutetium radical and its related compounds: the application of localized orbital basis set to open-shell phthalocyanine dimers

Abstract

The ground state and the lowest excited states of lutetium phthalocyanine dimer radical, [Lu(Pc)2] (Pc: phthalocyanine), and those of related compounds, [Lu(Nc)2] and [Lu(Nc)(Pc)] (Nc: 2,3-naphthalocyanine), are studied by configuration interaction calculations on localized orbital basis set. The orbitals, which are localized on either of two ligands, are obtained by a unitary transformation of semiempirical SCMOs of the dimer. The lowest three bands (7 X 10\ 10 X 103, and 15 X 103 cm-1 for [Lu(Pc)2]; 6 X 103, 8 X 103, and 13 X 103 cm"1 for [Lu(Nc)2]) are assigned to the excited states IB, (|G*)), 2E, (|D->) and 3Ei (|S->), respectively.The ground state of the C* heterodimer, [Lu(Nc)(Pc)], has a population of a hole more in the Nc ring than in the Pc ring. The population shifts toward Pc in the 2A2 excited state.

Magnetic circular dichroism and absorption spectra of lutetium bis(phthalocyanine) isolated in an argon matrix

“…Our approach also parallels that of Ishikawa et al 26,30 in that molecular states are described using localized orbitals on each ring. However, these workers couple a valence-bond-like basis on each ring to form molecular states, while we form symmetryadapted MOs (Dw) from the MOs (D4h) of the two rings.…”

The optical limiting of blue and green ytterbium double-decker phthalocyanines in solution and in poly(acrylic acid) as thin films

“…Such changes have been observed as a split Q band [41]. The characteristic absorption band in the 400-500 nm region for the green (neutral) form is referred to as the blue valence (BV) [42][43][44][45] or the blue vibronic band [40] resulting from various transitions which are forbidden in the idealized D 4h or D 4d symmetry [46][47][48]. As can be seen for 2a in Fig.…”

Influence of blue valence absorption band on nonlinear absorption in dysprosium bisphthalocyanine studied by open aperture z-scan

“…The inset of Figure 1 shows the energy molecular orbital diagram which has been constructed in accordance with Refs. [17][18][19][20][21]. The transition from the HOMO 2b 1 to the LUMO 6e 3 gives the main contribution to the Q band (670 nm).…”