scholarly journals Naphthyl-Fused Phosphepines: Luminescent Contorted Polycyclic P-Heterocycles

2019 ◽  
Author(s):  
Thomas Delouche ◽  
Réka Mokrai ◽  
Thierry Roisnel ◽  
Denis Tondelier ◽  
Bernard Geffroy ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Phosphine Oxide ◽  
Steric Hindrance ◽  
Building Blocks ◽  
Redox Properties ◽  
Substitution Reactions ◽  
Pi Conjugated ◽  
New Family ◽  
Pi Systems

The article presents the synthesis of a new family of naphthyl-fused phosphepines through Ni-mediated C-C coupling. Interestingly, the chloro-phosphine-oxide intermediate shows strong resistance toward oxidation/hydrolysis due to a combination of steric hindrance and pnictogen interactions. However it can undergo substitution reactions under specific conditions. The optical / redox properties and the electronic structure of these new pi-systems were studied experimentally and computationally. Taking advantage of the luminescence of these derivatives, a blue emitting OLED has been prepared highlighting that these novel pi-conjugated P-heterocycles appear as promising building blocks for solid-state lightning applications.

scholarly journals Naphthyl-Fused Phosphepines: Luminescent Contorted Polycyclic P-Heterocycles

2019 ◽  
Author(s):  
Thomas Delouche ◽  
Réka Mokrai ◽  
Thierry Roisnel ◽  
Denis Tondelier ◽  
Bernard Geffroy ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Phosphine Oxide ◽  
Steric Hindrance ◽  
Building Blocks ◽  
Redox Properties ◽  
Substitution Reactions ◽  
Pi Conjugated ◽  
New Family ◽  
Pi Systems

The article presents the synthesis of a new family of naphthyl-fused phosphepines through Ni-mediated C-C coupling. Interestingly, the chloro-phosphine-oxide intermediate shows strong resistance toward oxidation/hydrolysis due to a combination of steric hindrance and pnictogen interactions. However it can undergo substitution reactions under specific conditions. The optical / redox properties and the electronic structure of these new pi-systems were studied experimentally and computationally. Taking advantage of the luminescence of these derivatives, a blue emitting OLED has been prepared highlighting that these novel pi-conjugated P-heterocycles appear as promising building blocks for solid-state lightning applications.

scholarly journals From the Superatom to a Large Variety of Supermaterials: A Theoretical Study

2021 ◽  
Author(s):  
◽  
Julia Schacht
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Transition Metal ◽  
Gold Cluster ◽  
Functional Materials ◽  
Building Blocks ◽  
Factors Affecting ◽  
Solid State Materials ◽  
The Stability ◽  
The Individual

<p>Metal clusters have been a subject of interdisciplinary research for many years as they act as a bridge between atoms and solid-state materials. In particular, clusters that show distinct thermodynamic stability and unusual atom like behavior, with an electronic shell structure that exhibits a superatomic nature, have attracted considerable attention. The concept of clusters behaving as individual atoms and furthermore mimicking the chemistry of specific elements directly leads to the idea of using those nanoparticles as building blocks for new functional materials. Furthermore, it is interesting that one can change the properties of cluster assembled materials by solely changing the properties of the individual clusters involved.  In this work, various factors affecting superatomic assemblies are identified and critically analyzed within the means of first-principles computations. The icosahedral gold cluster Au₁₃[RS(AuSR)₂]₆ has been chosen as a model system to study the tunability of the electronic structure using single atomic impurities. In this context the doped clusters were found to be tunable such, that they reveal atomic properties, e.g. electron affinities similar to individual halogen atoms. In addition, the choice of ligands protecting the clusters is evaluated regarding the stability of the whole cluster and the involvement of the ligands in creating the superatomic structure. The latter was found to be important when thinking of orbital overlap in superatomic assemblies.  In a next step the knowledge gained is used to investigate cluster-cluster interactions and detect pairs of clusters that are good candidates to create new superatomic materials. Furthermore basic principles regarding cluster assemblies are established and partially tested in an experimental collaboration studing the structure of an Au₉(PPh₃)₈-C₆₀ assembly.  Beyond the investigation of individual gold clusters and gold cluster materials, the electronic structure of binary solid state materials consisting of ligand protected transition metal-chalcogen clusters and fullerenes, as synthesized by Roy et al., is presented. This study shows an intermediate case of non-tunable clusters and furthermore displays the partial loss of the superatomic character of the transition metal chalcogen clusters due to charge transfer.  An experimental collaboration conducted in cooperation with the research group of Prof. Beate Paulus in Berlin proceeds even further and investigates the absorption of water on non-superatomic aluminumoxo fluoride clusters.</p>

scholarly journals From the Superatom to a Large Variety of Supermaterials: A Theoretical Study

2021 ◽  
Author(s):  
◽  
Julia Schacht
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Transition Metal ◽  
Gold Cluster ◽  
Functional Materials ◽  
Building Blocks ◽  
Factors Affecting ◽  
Solid State Materials ◽  
The Stability ◽  
The Individual

<p>Metal clusters have been a subject of interdisciplinary research for many years as they act as a bridge between atoms and solid-state materials. In particular, clusters that show distinct thermodynamic stability and unusual atom like behavior, with an electronic shell structure that exhibits a superatomic nature, have attracted considerable attention. The concept of clusters behaving as individual atoms and furthermore mimicking the chemistry of specific elements directly leads to the idea of using those nanoparticles as building blocks for new functional materials. Furthermore, it is interesting that one can change the properties of cluster assembled materials by solely changing the properties of the individual clusters involved.  In this work, various factors affecting superatomic assemblies are identified and critically analyzed within the means of first-principles computations. The icosahedral gold cluster Au₁₃[RS(AuSR)₂]₆ has been chosen as a model system to study the tunability of the electronic structure using single atomic impurities. In this context the doped clusters were found to be tunable such, that they reveal atomic properties, e.g. electron affinities similar to individual halogen atoms. In addition, the choice of ligands protecting the clusters is evaluated regarding the stability of the whole cluster and the involvement of the ligands in creating the superatomic structure. The latter was found to be important when thinking of orbital overlap in superatomic assemblies.  In a next step the knowledge gained is used to investigate cluster-cluster interactions and detect pairs of clusters that are good candidates to create new superatomic materials. Furthermore basic principles regarding cluster assemblies are established and partially tested in an experimental collaboration studing the structure of an Au₉(PPh₃)₈-C₆₀ assembly.  Beyond the investigation of individual gold clusters and gold cluster materials, the electronic structure of binary solid state materials consisting of ligand protected transition metal-chalcogen clusters and fullerenes, as synthesized by Roy et al., is presented. This study shows an intermediate case of non-tunable clusters and furthermore displays the partial loss of the superatomic character of the transition metal chalcogen clusters due to charge transfer.  An experimental collaboration conducted in cooperation with the research group of Prof. Beate Paulus in Berlin proceeds even further and investigates the absorption of water on non-superatomic aluminumoxo fluoride clusters.</p>

scholarly journals Supramolecular organic frameworks (SOFs): homogeneous regular 2D and 3D pores in water

2017 ◽  
Vol 4 (3) ◽  
pp. 426-436 ◽  
Author(s):  
Jia Tian ◽  
Hui Wang ◽  
Dan-Wei Zhang ◽  
Yi Liu ◽  
Zhan-Ting Li
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Organic Dyes ◽  
Three Dimensional ◽  
Building Blocks ◽  
Future Research ◽  
New Family ◽  
Molecular Building Blocks ◽  
Anionic Species ◽  
2D And 3D

Abstract Studies on periodic porosity and related properties and functions have been limited to insoluble solid-state materials. Self-assembly provides a straightforward and efficient strategy for the construction of soluble periodic porous supramolecular organic frameworks (SOFs) in water from rationally designed molecular building blocks. From rigid tri- and tetra-armed building blocks and cucurbitu[8]ril (CB[8]), a number of two-dimensional (2D) honeycomb, square and rhombic SOFs can be generated, which is driven by CB[8]-encapsulation-enhanced dimerization of two aromatic units on the periphery of the multi-armed molecules. By utilizing the same three-component host−guest motif as the driving force, three-dimensional (3D) diamondoid and cubic SOFs can be obtained from tetrahedral and [Ru(bipy)3]2+-derived octahedral monomers and CB[8]. All of the 2D and 3D periodic frameworks are soluble in water, and are able to maintain the periodicity as well as the pore sizes in the solid state. 3D SOFs are highly efficient homogeneous polycationic frameworks for reversible adsorption of anionic species including organic dyes, peptides, nucleic acids, drugs, dendrimers and Wells-Dawson-typed polyoxametallates (WD-POMs). WD-POM molecules adsorbed in the [Ru(bipy)3]2+-based SOF can catalyse the reduction of proton to H2 upon visible-light sensitization of [Ru(bipy)3]2+, which allows multiple electron transfer from [Ru(bipy)3]2+ to WD-POM. This review summarizes the design, formation and characterization of this new family of self-assembled frameworks, highlights their applications as homogeneous porous materials and finally outlines some future research directions.

scholarly journals Fluorinated azobenzenes as supramolecular halogen-bonding building blocks

2019 ◽  
Vol 15 ◽  
pp. 2013-2019 ◽  
Author(s):  
Esther Nieland ◽  
Oliver Weingart ◽  
Bernd M Schmidt
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Visible Light ◽  
Half Life ◽  
Photophysical Properties ◽  
Bathochromic Shift ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Partial Overlap

ortho-Fluoroazobenzenes are a remarkable example of bistable photoswitches, addressable by visible light. Symmetrical, highly fluorinated azobenzenes bearing an iodine substituent in para-position were shown to be suitable supramolecular building blocks both in solution and in the solid state in combination with neutral halogen bonding acceptors, such as lutidines. Therefore, we investigate the photochemistry of a series of azobenzene photoswitches. Upon introduction of iodoethynyl groups, the halogen bonding donor properties are significantly strengthened in solution. However, the bathochromic shift of the π→π* band leads to a partial overlap with the n→π* band, making it slightly more difficult to address. The introduction of iodine substituents is furthermore accompanied with a diminishing thermal half-life. A series of three azobenzenes with different halogen bonding donor properties are discussed in relation to their changing photophysical properties, rationalized by DFT calculations.

ChemInform Abstract: Electronic Structure of Thiacyanine Dyes (I) in the Solid State

ChemInform ◽  
1989 ◽  
Vol 20 (35) ◽  
Author(s):  
T. B. TANG ◽  
H. YAMAMOTO ◽  
K. IMAEDA ◽  
H. INOKUCHI ◽  
K. SEKI ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Solid State

First principles study on the electronic structure properties of Keggin polyoxometalates on Carbon substrates for solid-state devices

2017 ◽  
Vol 136 (2) ◽  
Author(s):  
Jesús Muñiz ◽  
Christian Celaya ◽  
Ana Mejía-Ozuna ◽  
Ana Karina Cuentas-Gallegos ◽  
L. M. Mejía-Mendoza ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
First Principles ◽  
First Principles Study ◽  
Solid State Devices ◽  
Carbon Substrates ◽  
Structure Properties

Tri(tert-butyl)phosphinoxid, -imin, -methylen und -boran / Tri(tert-butyl)phosphine Oxide, Imine, Methylene and Borane

1978 ◽  
Vol 33 (12) ◽  
pp. 1556-1558 ◽  
Author(s):  
Hubert Schmidbaur ◽  
Günter Blaschke
Keyword(s):  
Thermal Decomposition ◽  
Phosphine Oxide ◽  
Steric Hindrance ◽  
Reductive Elimination ◽  
Tert Butyl

Abstract Tri(tert-butyl)phosphine Oxide, Imine, Methylene, Borane Tri(tert-butyl)phosphine oxide, imine, methylene and borane have been prepared and their properties investigated. The imine is chemically inert due to strong steric hindrance. Its thermal decomposition at 200 °C leads to tri(tert-butyl)-pliosphine, in contrast to the methylene analogue which undergoes reductive elimination of isobutene. Both the oxide and borane are thermally very stable (> 250 °C).

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