Ternary Iodido Bismuthates and the Special Role of Copper

Dehnhardt, Natalie; Borkowski, Hendrik; Schepp, Johanna; Tonner, Ralf; Heine, Johanna

doi:10.1021/acs.inorgchem.7b02418

Cited by 32 publications

(36 citation statements)

References 88 publications

(90 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A specifically suitable method for bonding analysis in the solid is the crystal orbital Hamilton population (COHP) analysis that delivers quantitative characterization of bonding, non‐bonding and anti‐bonding interatomic interactions . All these methods can be combined for a full understanding of the metal‐dependent band gaps ( E g ) as shown for metalla iodido bismuthates [PPh 4 ] 4 [MBi 2 I 12 ] ( E g = 1.8 eV for M = Cu; E g = 2.1 eV for Ag)—possible nontoxic alternatives to lead‐based perovskites in solar cell applications . Solid‐state computations with and without spin–orbit coupling indicated a strong influence of relativistic effects on the bonding in these compounds.…”

Section: Bonding In Solidsmentioning

confidence: 99%

See 1 more Smart Citation

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Pecher

Tonner

2018

WIREs Comput Mol Sci

Self Cite

View full text Add to dashboard Cite

Chemical bonding concepts like covalency, ionicity, Pauli repulsion, shared-electron, or donor-acceptor bonding are important tools to sort our vast knowledge in chemistry and predict new reactivity. Electronic structure analysis provides the basis for a detailed understanding of the origins of these concepts. Energy decomposition analysis (EDA) is an established method for molecules and has recently been implemented for application in extended systems, that is, surfaces and solids, where it is termed periodic EDA (pEDA). The foundations and applications of this method which enables the derivation of bonding concepts are outlined in this review. Embedded in key examples from molecular and solid-state chemistry, the major part covers the adsorption and reactivity of molecules with surfaces with a focus on organic molecules interacting with semiconductor surfaces. Based on electronic structure analysis and supported by a quantitative methodology, we show that analogous bonding concepts can be applied in diverse chemical environments. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Structure and Mechanism > Computational Materials Science K E Y W O R D S chemical bonding, density functional theory, energy decomposition analysis, surface chemistry 1 | INTRODUCTIONThe chemical bond is the central concept in the discussion of structures and reactivity in chemistry. The nature of the forces that hold atoms together thrills chemists since the upcoming of atomistic theories. First realistic models were derived more than two centuries ago based on experimental observations. 1 The paradigm shift at the beginning of the 20th century then provided the basis for our present-day understanding of chemical bonding in terms of quantum mechanical principles. 2,3 But by no means did this development end the discussion about chemical bonding and the interpretation of results obtained by theory and computation. The intrinsic ambiguity in discussing often nonobservable properties that are connected to very useful concepts like covalency, ionicity, Pauli repulsion, bond order, and alike fosters the scientific discussion and leads to a further refinement of our understanding of the chemical bond. [4][5][6][7][8][9][10][11] The development of bonding concepts in molecular and solid-state chemistry evolved separately for the most part. For molecules, the view on (more or less) localized bonds as given by the Lewis picture more than a century ago 12 was regained both by valence bond (VB) theory and from the molecular orbital (MO) approach by the linear combination of atomic orbitals (LCAO) and localization procedures. [13][14][15][16] This resulted in the development of many powerful methods for electronic structure analysis for the qualitative and quantitative interpretation of chemical bonding that have been summarized in previous reviews. 2,17-21 Some examples will be discussed in the next section. In the field of surfaces and solids, the delocalized view

show abstract

Section: Bonding In Solidsmentioning

confidence: 99%

“…(c,d) Corresponding density of states (DOS) with partial DOS (pDOS) for Cu or Ag and Bi with and without (nr‐pDOS) spin–orbit coupling. (Reprinted with permission from Reference . Copyright 2018 American Chemical Society)…”

Section: Bonding In Solidsmentioning

confidence: 99%

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Pecher

Tonner

2018

WIREs Comput Mol Sci

Self Cite

View full text Add to dashboard Cite

show abstract

“…This can mainly be ascribed to the existence of BO 6 octahedra where electronic states of the B and O atoms play dominant roles in the conduction and valence band edges, respectively. Consequently, this provides huge opportunities to considerably alter the physical properties of these materials through chemical as well as physical means [17][18] . In particular, strontium titanate (SrTiO 3 ), barium titanate (BaTiO 3 ), strontium zirconate (SrZrO 3 ) and barium zirconate (BaZrO 3 ) are important perovskite oxides where 3d and 4d electrons of Ti and Zr, respectively, are bonded with the 2p electrons of oxygen.…”

Section: Introductionmentioning

confidence: 99%

Revisiting the structural, electronic and photocatalytic properties of Ti and Zr based perovskites with meta-GGA functionals of DFT

et al. 2021

View full text Add to dashboard Cite

show abstract

“…These materials, as well as the reported [(Me) 3 (4‐TPT)] 2 [Cu 12 I 18 ], [Pb 5 Cu 2 I 16 ][(Me) 2 (4‐TPT)] 2 , [Pb 3 Cu 6 I 14 ] [(Me) 3 (4‐TPT)] 2 and [Me 3 (4‐TPT)][Cu 5 I 8 ], possess narrow band gaps of 1.02–2.19 eV. The values are comparable to those of organic ammoniums or metal complex templated halide hybrids, which feature small band gaps and exhibit attractive optoelectronic properties. Therefore, we are delighted to discover that introducing N ‐alkylation TPT‐derivatives as SDAs in halides may be an effective synthetic strategy for regulating electronic band structures, which can decrease the band gap and accordingly increase visible‐light absorption.…”

Section: Resultsmentioning

confidence: 99%

Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance

Wei

Zhang

et al. 2018

Chemistry An Asian Journal

View full text Add to dashboard Cite

Through regulating the pH values, a series of iodo‐argentate/cuprate hybrids, [Me3(4‐TPT)]4[Ag6I18] (1, Me3(4‐TPT)=N,N′,N′′‐trimethyl‐2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine), [Me3(4‐TPT)][M5I8] (M=Ag/2, Cu/2 a), [Me3(3‐TPT)][M5I8] (Me3(3‐TPT)=N,N′,N′′‐trimethyl‐2,4,6‐tris(3‐pyridyl)‐1,3,5‐triazine, M=Ag/3, Cu/4), which exhibit adjustable structural variations with different dimensional structures, have been obtained under solvothermal conditions. They are directed by two types of in situ N‐alkylation TPT‐derivatives (Me3(4‐TPT) for 1/2/2 a and Me3(3‐TPT) for 3/4) and represent the isolated units (1), 1D polymeric chain (4), 2D layered structures (2/2 a, 3) based on diverse metal iodide clusters. These compounds possess reducing band gaps as compared with the bulk β‐AgI and CuI and belong to potential semiconductor materials. Iodocuprates feature highly efficient photocatalytic activity in the sunlight‐induced degradation of organic dyes. The detailed study on the possible photocatalytic mechanism, including radical trapping tests and theoretical calculations, reveals that the N‐alkylation TPT moieties contribute to the narrow semiconducting behavior and effectively inhibit the recombination of photogenerated electron‐hole pairs, which result in an excellent visible‐light‐induced photocatalytic performance.

show abstract

Ternary Iodido Bismuthates and the Special Role of Copper

Cited by 32 publications

References 88 publications

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Revisiting the structural, electronic and photocatalytic properties of Ti and Zr based perovskites with meta-GGA functionals of DFT

Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance

Contact Info

Product

Resources

About