We demonstrate the feasibility of hexacoordinate silicon complexes with dianionic pincer ligands as electron transport and electroluminescent components of organic electronic devices.

Organic−inorganic hybrids may offer material properties not available from their inorganic components. However, they are typically less stable and disordered. Long-term stability study of the hybrid materials, over the anticipated lifespan of a real-world electronic device, is practically nonexistent. Disordering, prevalent in most nanostructure assemblies, is a prominent adversary to quantum coherence. A family of perfectly ordered II−VI-based hybrid nanostructures has been shown to possess many unusual properties and potential applications. Here, using a prototype structure β-ZnTe(en) 0.5 a hybrid superlatticeand applying an array of optical, structural, surface, thermal, and electrical characterization techniques, in conjunction with densityfunctional theory calculations, we have performed a comprehensive and correlative study of the crystalline quality, structural degradation, electronic, optical, and transport properties on samples from over 15 years old to the recently synthesized. The findings show that not only do they exhibit an exceptionally high level of crystallinity in both macroscopic and microscopic scale, comparable to high-quality binary semiconductors; and greatly enhanced material properties, compared to those of the inorganic constituents; but also, some of them over 15 years old remain as good in structure and property as freshly made ones. This study reveals (1) what level of structural perfectness is achievable in a complex organic−inorganic hybrid structure or a man-made superlattice, suggesting a nontraditional strategy to make periodically stacked heterostructures with abrupt interfaces; and (2) how the stability of a hybrid material is affected differently by its intrinsic attributes, primarily formation energy, and continued...

Fundamental properties of conjugated copolymers are sensitively linked to their constitution and features of their repeat unit design that govern assembly and organization across multiple length scales, ultimately impacting device...

Hexacoordinate silicon pincer complexes using 2,6-bis(benzimidizol-2-yl)pyridine (bzimpy) ligands have been developed as a multifunctional, molecular electronic materials platform. We report the synthesis, characterization, and device application of a variety of...

The design of metal-organic frameworks (MOFs) that incorporate more than one metal cluster constituent is ac hallenging task. Conventionalo ne-pot reactionp rotocols requirej udiciouss election of ligand and metal ion precursors, yet remainu npredictable. Stable, preformed nanoclusters, with ligand shells that can undergo additional coordination-driven reactions, provide ap latform for assembling multi-cluster solids with precision.H erein, ad iscrete Co 6 S 8 (PTA) 6 (PTA = 1,3,5-triaza-7-phosphaadamantane) superatomic-metalloligand is assembled into a three-dimensional (3D) coordination polymer comprising Cu 4 I 4 secondary building units (SBUs). The resulting heterobimetallic framework (1)c ontains two distinct cluster constituents and bifunctional PTAl inkers. Solid-state diffuse reflectances tudies revealt hat 1 is an optical semiconductor with ab and-gap of 1.59 eV.F ramework-modified electrodes exhibit reversible redox behaviori nt he solid state arising from the Co 6 S 8 superatoms, which remain intact during framework synthesis.

A C/Si switch provides easy access to polybrominated spirosilabifluorenes with tailorable regioselectivities. Yamamoto coupling leads to fluorescent microporous materials that can act as a sensor for nitroaromatics.

Si(bzimpy) 2 , a fluorescent organic complex, has been demonstrated as a potential electron transport and electroluminescent layer for organic electronic devices. Despite the successful synthesis and encouraging electroluminescence at 560 nm, the complex dielectric function of the water-stable complex has not been reported yet. In this letter, we report on the first spectroscopic ellipsometry data obtained from a Si(bzimpy) 2 thin film in the spectral range from 300 nm to 1900 nm (0.65 eV to 4.1 eV). A parameterized model dielectric function composed of a Tauc-Lorentz and Gaussian oscillators is employed to analyze the experimental ellipsometry data. We find a good agreement between the absorption energies observed experimentally here and density functional theory calculations reported earlier.

Organic–inorganic hybrid materials often face a stability challenge. β‐ZnTe(en)0.5, which uniquely has over 15‐year real‐time degradation data, is taken as a prototype structure to demonstrate an accelerated thermal aging method for assessing the intrinsic and ambient‐condition long‐term stability of hybrid materials. Micro‐Raman spectroscopy is used to investigate the thermal degradation of β‐ZnTe(en)0.5 in a protected condition and in air by monitoring the temperature dependences of the intrinsic and degradation‐product Raman modes. First, to understand the intrinsic degradation mechanism, the transition state of the degradation is identified, then using a density functional theory, the intrinsic energy barrier between the transition state and ground state is calculated to be 1.70 eV, in excellent agreement with the measured thermal degradation barrier of 1.62 eV in N2 environment. Second, for the ambient‐condition degradation, a reduced thermal activation barrier of 0.92 eV is obtained due to oxidation, corresponding to a projected ambient half‐life of 40 years at room temperature, in general agreement with the experimental observation of no apparent degradation over 15 years. Furthermore, the study reveals a mechanism, conformation distortion enhanced stability, which plays a pivotal role in forming the high kinetic barrier, contributing greatly to the impressive long‐term stability of β‐ZnTe(en)0.5.