Theoretical study on the charge transport property of Pt(CNtBu)2(CN)2 nanowires induced by Pt⋯Pt interactions

Abstract

To deeply understand the charge-transporting nature of Pt(CN(t)Bu)(2)(CN)(2) nanowires induced by intermolecular Pt···Pt interactions, calculations based on first-principle band structure and Marcus theory have been performed. The calculated bandwidths of the valence band, conducting band, and the effective masses of hole and electron are almost equal. This suggests that this complex has ambipolar transport characteristics, in agreement with experimental results. Density of states analysis revealed that the hole transport resulted mainly from the Pt···Pt interactions, while the electron transport was derived mainly from the CN groups. The character of the frontier molecular orbitals, reorganization energies and transfer integrals in different directions also supports the calculated first-principle band structure. Moreover, an investigation into the intermolecular interaction energy of neighbors revealed that there is a remarkable relationship between the intermolecular interaction energy and the transfer integral.

Synergistic π–π and Pt–Pt interactions in luminescent hybrid inorganic/organic dual columnar liquid crystals

“…For example, some Pt II complexes that form 1D micro and nanowires, 23 display semiconducting properties. 62 Furthermore, some halogen-bridged mixed-valence platinum complexes, display metallic conductivity at room temperature. 63,64 Conduction might occur in our materials through three different ways: a) along the stack of the triphenylene organic groups; b) along the columns of the organometallic platinum-benzoquinolate fragments with Pt···Pt interactions, which is our main interest; and c) since it is an ionic system, through ionic conduction.…”

Fast‐Response, Highly Air‐Stable, and Water‐Resistant Organic Photodetectors Based on a Single‐Crystal Pt Complex

“…However, the important device characteristics (such as mobility, photoresponsivity, and response time) can be further improved by adding functional molecular structures to the crystal . We also note that the quasilinear Pt⋅⋅⋅Pt⋅⋅⋅Pt interaction promotes high hole transfer integral along the π–π stacking direction, as revealed by theoretical calculations . The change in transfer integral along different axes suggests that the single‐crystal Pt complex may behave as an ambipolar semiconductor, thus it requires further study which lies beyond the scope of the present work.…”

“…[61] We also note that the quasilinear Pt⋅⋅⋅Pt⋅⋅⋅Pt interaction promotes high hole transfer integral along the π-π stacking direction, as revealed by theoretical calculations. [62] The change in transfer integral along different axes suggests that the singlecrystal Pt complex may behave as an ambipolar semiconductor, thus it requires further study which lies beyond the scope of the pre sent work.…”

Geometrical manipulation of complex supramolecular tessellations by hierarchical assembly of amphiphilic platinum(II) complexes

“…The present work illustrates the formation of complex self-assembled architectures based on geometrically simple molecules, thus expanding the library of building motifs and the fundamental understanding of the structural order and molecular organization in soft materials. It is envisaged that the present soft materials with well-organized molecular packing hold promise for the development of high-performance electronic devices based on Pt II complexes (55)(56)(57).…”