Structural regularity and diversity in hybrids of aromatic thioethers and BiBr3: from discrete complexes to layers and 3D nets

Abstract

This paper aims to explore the regular structural patterns and the associated electronic properties of a group of hybrid networks based on BiBr3 and aromatic thioethers, with emphasis on structurally correlating the organic molecules with the BiBr3 aggregates as well as the overall hybrid networks. It was found that extended BiBr3 chains tend to be associated with the slender 4-methylthiophenylalkynyl units, whereas biaryl-based molecules with 4-MeSPh groups directly linked to aromatic cores form hybrids with discrete BiBr3 clusters of variable nuclearities and connectivities. By using multidentate ligands with open geometries, this exploratory study also achieves hybrid BiBr3-aromatic thioether networks with open framework and higher dimensional (e.g., 3D) features, which are potentially amenable to further study on guest exchange experiments. Diffuse reflectance measurements on the powder samples of the hybrids and the organic molecules reveal significant electronic interactions between the inorganic and organic components, with the absorption edges of the hybrids uniformly shifted to lower energies relative to the organic samples. In systems with similar network connectivity and local bonding features, the shifts appear to be proportional to the absorption energy of the organic molecules, suggesting that, in a first order approximation, the absorption edge in the hybrids involves substantially the electronic transitions from the HOMOs of the organic molecules to the LUMOs (or conduction bands) of the inorganic components.

A New Class of Nanostructured Inorganic–Organic Hybrid Semiconductors Based on II–VI Binary Compounds

“…The layered perovskite hybrid structures provide a good platform for the preparation and investigation of two-dimensional (2D) quantum well systems (89)(90)(91)(92). A number of interesting optical, electrical, and magnetic properties have been discovered in these materials (75,90,(93)(94)(95)(96)(97)(98)(99)(100)(101)(102)(103)(104)(105)(106)(107)(108).…”

Star-Shaped Conjugated Systems

“…1,2,4,5-Tetrakis(oligophenylene)benzene Derivatives (C-5-A-3) : The rigid and shape-persistent structure of tetraphenylbenzene was exploited as building blocks for MOFs (compound 55c ( n = 1, E = SCH 3 ), 55d (n = 1, E = COOH)) [171,172,173,174,175,176] and in crystal engineering by hydrogenbonds ( 55e , n = 1, E = diaminotriazinyl) [177]. For example 55d complexed to Zn(NO 2 ) 2 was tailored to uptake a remarkable amount of cryogenic hydrogen [174] and could also be postsynthetically modified to adsorb CO 2 [175].…”

“…1,2,4,5-Tetrakis(oligo(phenylene ethynylene))benzenes (C-5-A-8): In contrast, to the stilbenoid compounds 56 , 1,2,4,5-tetrakis(oligo(phenylene ethynylen))benzenes 57 can be classified as shape-persistent compounds and consequently a methylsulfanyl capped derivatives was applied to form 2D and 3D networks with BiBr 3 [171]. Methylsulfanyl and methylsulfanylethynyl capped derivatives have been also employed to mediate the self-assembly of gold nanoparticles [186].…”

“…The latter is a feature of interest in the design of coordination networks, which has been attempted for 129a (E = SCH 3 ) with BiBr 3 [171] and AgOTf. [333] Only the latter salt resulted in the formation of a 3D network.…”

DFT and TD‐DFT Study of Structure and Properties of Semiconductive Hybrid Networks Formed by Bismuth Halides and Different Polycyclic Aromatic Ligands

“…Structure of the organic ligands with atom labelling Do the solid-state electronic properties depend on nature of bond coordination of Bi-S and Bi-X of such systems. What is the correlation between band gap and dimensionality 17 . A large number of density functional theory (DFT) studies have treated excited state properties based on the time-dependent (TD) method.…”