Modulation of Band Gaps toward Varying Conductivities in Heterometallic One-Dimensional Chains by Ligand Alteration and Third Metal Insertion.

A heterometallic one-dimensional (1-D) chain consisting of multiple kinds of metals, Rh, Pt, and Pd, with direct metal-metal bonds was successfully obtained by mixing a Rh dinuclear complex and Pt-Pd-Pt trinuclear complex. The Pt-Pd-Pt trinuclear complex can be reversibly one-electron-oxidized or -reduced, where the electron paramagnetic resonance spectrum of the one-electron-oxidized one shows an axially symmetric signal with hyperfine splitting by two Pt and Pd, indicating that an unpaired electron is delocalized to the d orbital of Pt-Pd-Pt. Utilized with the highest occupied molecular orbital and lowest unoccupied molecular orbital interaction at the d orbital, simple mixing of the Pt-Pd-Pt trinuclear complex and Rh dinuclear complex in adequate solvents afforded heterometallic 1-D chains, which are aligned as -Rh-Rh-Pt-Pd-Pt-. Several physical measurements revealed that the metal oxidation state is +2. Diffuse reflectance spectra and theoretical calculations show that heterometallic 1-D chains have σ-type conduction and valence bands where π*(Rh) are lying between them, whose gaps become narrower than the prototype chains aligned as -Rh-Rh-Pt-Pt-Pt-Pt-. The narrower band gaps are induced by destabilization of the σ-type valence bands and accompanied by insertion of Pd ions because the d-orbital energy level of Pd is closer in value to Rh compared with Pt. Flash-photolysis time-resolved microwave conductivity measurements exhibited an increase in the product of charge carrier mobility and its generation efficiency (8.1 × 10 to 4.6 × 10 cm V s) with narrowing the band gaps, suggesting that the better conductivity is attributed to shorter metal-metal distances in 1-D chains. These results imply the possibilities of controlling band gap with ligand modification and third metal insertion in heterometallic 1-D chains to show various conductivities.