Diradical character and nonlinear optical properties of buckyferrocenes: focusing on the use of suitably modified fullerene fragments.

The buckyferrocenes, synthesized through face-to-face fusion of ferrocene and fullerene fragments (C₆₀Me₁₀), are expected to enjoy the rich scientific heritage of ferrocene and fullerene with an extensively large π-conjugation network between the two Fe atoms [Y. Matsuo, K. Tahara and E. Nakamura, J. Am. Chem. Soc., 2006, 128, 7154]. However, the addition of pentamethyl groups at each end of the fullerene fragment breaks the π-conjugation path as well as metal–metal spin correlation between the two-ferrocene faces in a buckyferrocene. We found that the unblocking of π-conjugation from different positions in fullerene fragments have substantial effects on their topologies, spin densities, diradical characters as well as nonlinear optical (NLO) properties of these buckyferrocenes. We study the topological dependence of open-shell diradical character and second hyperpolarizability (γ), the third-order NLO properties at the molecular scale, in several buckyferrocenes. On the basis of their different diradical characters (y_i), which are defined by the occupation number of the lowest unoccupied natural orbital (LUNO) + i (i = 0, 1,…), these buckyferrocenes are categorized into three groups, i.e., closed-shell (y_i = 0), intermediate open-shell singlet (0 ＜ y_i ＜ 1), and almost pure open-shell singlet (y_i = 1) compounds. For example, we found that buckyferrocenes including (CpFe)₂η⁵C₆₀Me₁₀ and (CpFe)₂η⁵C₇₀Me₁₀ have closed-shell configurations. The buckyferrocenes (CpFe)₂η⁵C₆₀, (CpFe)₂η⁵C₇₀, (CpFe)₂η⁵C₇₀Me₈, (CpFe)₂η⁵C₇₀Me₄ and (CpFe)₂η⁵C₃₀ are intermediate open-shell singlet, while (CpFe)₂η⁵C₆₀Me₄ and (CpFe)₂η⁵C₆₀Me₈ are pure open-shell singlet complexes. Interestingly, the γ_zzzz amplitude of (CpFe)₂η⁵C₆₀, an open-shell intermediate diradical complex, is about 41 times and 13 times as large as those of its closed-shell ((CpFe)₂η⁵C₆₀Me₁₀) and pure diradical ((CpFe)₂η⁵C₆₀Me₈) counterparts, respectively. Similarly, the γ_zzzz amplitudes of (CpFe)₂η⁵C₇₀, (CpFe)₂η⁵C₇₀Me₄, and (CpFe)₂η⁵C₇₀Me₈ with intermediate diradical character are about 36, 17, and 9 times as large as that of their closed-shell (CpFe)₂η⁵C₇₀Me₁₀ counterpart. The fact that larger γ_zzzz values are obtained for buckyferrocenes with intermediate diradical characters is in line with the “y–γ correlation” obtained from the valence configuration interaction (VCI) results for a two-site diradical model [M. Nakano, et al., Phys. Rev. Lett., 2007, 99, 033001] as well as for fullerene and graphene systems. The γ_zzzz density analysis shows that the large positive contributions originate from the large γ_zzzz density distributions on the upper- and lower-extended edges of the buckyferrocenes, between which significant spin polarizations appear within the spin-unrestricted DFT level of theory. These results demonstrate that such buckyferrocenes are potential candidates for a novel class of open-shell singlet NLO systems, where γ_zzzz values are modulated by tuning their diradical character through the use of suitably modified fullerene fragments. [ABSTRACT FROM AUTHOR]