Synthesis of organic biaryl and aryl silyl ether linkers for surface functionalization of silicon semiconductors

Functional organic materials for use in inorganic semiconductor applications is of high scientific interest due to the need for flexible, conductive materials that can be utilized in solar energy applications. Herein is described a synthetic route for a new variant of biphenylene linker called 2Ldm-OTf-bpA, which can be used as a building block for future conductive oligophenylene materials in semiconductor devices. With unique ortho-functionalized dimethoxy handles and para-functionalization via triflate and bromo groups, this linker can be chemically modified at the bromo position to attach to silicon semiconductor surfaces. Additionally, a synthetic route for 1-LdSihex₃-OTf is presented which utilizes the modular synthon 1Ld-OH-OTf that can be synthetically modified to generate many variations of small molecules, which can be used to control the steric spacing of molecules on surfaces during functionalization. Conversely, the triflate group can be utilized as a synthetic modification point for future studies of molecular wire growth on silicon surfaces. These molecular wires will be the foundation of future studies for developing a hybrid molecular/materials (HMM) layer on Si(111). These surfaces can then act as anchor points for catalysts for the production of solar fuels conversion such as H₂ from water or the reduction of CO₂ to methanolChemistr

A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N₂: A Kinetic or Thermodynamic Impediment to N–N Bond Cleavage?

We report the first mononuclear three-coordinate vanadium­(II) complex [(nacnac)­V­(ODiiP)] and its activation of N₂ to form an end-on bridging dinitrogen complex with a topologically linear V­(III)­N₂V­(III) core and where each vanadium center antiferromagnetically couples to give a ground state singlet with an accessible triplet state as inferred by HFEPR spectroscopy. In addition to investigating the conversion of N₂ to the terminal nitride (as well as the microscopic reverse process), we discuss its similarities and contrasts to the isovalent <i>d</i>³ system, [Mo­(N­[^<i>t</i>Bu]­Ar)₃], and the <i>S</i> = 1 system [(Ar­[^<i>t</i>Bu]­N)₃Mo]₂(μ₂-η¹:η¹-N₂)

A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N₂: A Kinetic or Thermodynamic Impediment to N–N Bond Cleavage?

We report the first mononuclear three-coordinate vanadium­(II) complex [(nacnac)­V­(ODiiP)] and its activation of N₂ to form an end-on bridging dinitrogen complex with a topologically linear V­(III)­N₂V­(III) core and where each vanadium center antiferromagnetically couples to give a ground state singlet with an accessible triplet state as inferred by HFEPR spectroscopy. In addition to investigating the conversion of N₂ to the terminal nitride (as well as the microscopic reverse process), we discuss its similarities and contrasts to the isovalent <i>d</i>³ system, [Mo­(N­[^<i>t</i>Bu]­Ar)₃], and the <i>S</i> = 1 system [(Ar­[^<i>t</i>Bu]­N)₃Mo]₂(μ₂-η¹:η¹-N₂)

A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N₂: A Kinetic or Thermodynamic Impediment to N–N Bond Cleavage?

We report the first mononuclear three-coordinate vanadium­(II) complex [(nacnac)­V­(ODiiP)] and its activation of N₂ to form an end-on bridging dinitrogen complex with a topologically linear V­(III)­N₂V­(III) core and where each vanadium center antiferromagnetically couples to give a ground state singlet with an accessible triplet state as inferred by HFEPR spectroscopy. In addition to investigating the conversion of N₂ to the terminal nitride (as well as the microscopic reverse process), we discuss its similarities and contrasts to the isovalent <i>d</i>³ system, [Mo­(N­[^<i>t</i>Bu]­Ar)₃], and the <i>S</i> = 1 system [(Ar­[^<i>t</i>Bu]­N)₃Mo]₂(μ₂-η¹:η¹-N₂)