Monomeric thorium chalcogenolates with bipyridine and terpyridine ligands

2018 ◽  
Vol 47 (41) ◽  
pp. 14652-14661 ◽  
Author(s):  
Marissa Ringgold ◽  
Wen Wu ◽  
Matthew Stuber ◽  
Anna Y. Kornienko ◽  
Thomas J. Emge ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Ligand Charge Transfer ◽  
Charge Transfer Excitation ◽  
Terpyridine Ligands ◽  
Coordinate Structures

Thorium chalcogenolates react with bipyridine or terpyridine to form a series of chelate stabilized Th(ER)4 compounds (E = S, Se; R = Ph, C6F5). 77Se NMR shows that the eight coordinate structures are maintained in solution. These compounds are thermochromic, with color originating from a visible ligand to ligand charge transfer excitation.

Photodisproportionation of (1,5-Cyclooctadiene) copper(I) Hexafluoroacetylacetonate Induced by Metal-to-Ligand Charge Transfer Excitation

2003 ◽  
Vol 58 (7) ◽  
pp. 704-707 ◽  
Author(s):  
Horst Kunkely ◽  
Arnd Vogler
Keyword(s):  
Excited State ◽  
Charge Transfer ◽  
Quantum Yields ◽  
Long Wavelength ◽  
Ligand Charge Transfer ◽  
Elemental Copper ◽  
Charge Transfer Excitation ◽  
Reactive Excited State

The complex CuI(COD)(hfac) with COD = 1,5- cyclooctadiene and hfac = hexafluoroacetyl-acetonate shows two long-wavelength absorptions at λmax = 308 and 241 nm which are assigned to hfac intraligand (IL) and CuI →COD metal-to-ligand charge transfer (MLCT) transitions, respectively. The photolysis of CuI(COD)(hfac) in hexane leads to the release of the olefin and the subsequent disproportionation of CuI(hfac) to elemental copper and CuII(hfac)2 with the quantum yields Φ = 10−3 at λirr =313 nm and Φ = 3×10−3 at λirr = 254 nm. It is suggested that the reactive excited state is of the MLCT type.

Structure-Performance Correlations in Electrochromic Behaviors of Terpyridine-Metal Hybrid Materials

2016 ◽  
Vol 852 ◽  
pp. 156-163 ◽  
Author(s):  
Jia Wei Yang ◽  
Xian Ge Xie ◽  
Xiao Mei Wang ◽  
Chang Qing Ye ◽  
Yu Yang Zhou
Keyword(s):  
Molecular Structure ◽  
Charge Transfer ◽  
Metal Ions ◽  
Structure Property ◽  
Reversible Change ◽  
Absorption Intensity ◽  
Coloration Efficiency ◽  
Structure Property Relationships ◽  
Ligand Charge Transfer ◽  
Terpyridine Ligands

Exploring the structure-property relationships is a fundamental but significant work for the design of new molecular. Rationaly designing of electrochromic materials that can switch rapidly and durably requires sophisticated understanding of the correlations between molecular structure and the performance. This work presents four electro-polymerizable metallosupramolecular coordinations self-assembled from triphenylamine-based terpyridine ligands and metal ions (Fe2+, Ru2+). The polymerized metal complexes can exhibit reversible change of the metal-to-ligand charge transfer (MLCT) absorption intensity. Along with the increase of voltage, the intensity of MLCT absorption peaks gradually reduced to disappear. Structure/performance correlations in electrochromic performance, especially the influence of different ligands and metal ions upon the coloration efficiency have been discussed.

Photooxidation of Dicyanoaurate(I) Induced by Metal-to-Ligand Charge Transfer Excitation

1998 ◽  
Vol 53 (8) ◽  
pp. 853-855 ◽  
Author(s):  
Horst Kunkely ◽  
Arad Vogler
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Charge Transfer ◽  
Charge Transfer State ◽  
State Electron ◽  
Ligand Charge Transfer ◽  
Charge Transfer Excitation ◽  
Transfer State

Abstract The irradiation of [Au(CN)2]- in oxygen-saturated acetonitrile leads to photooxidation of Au(I). In the presence of additional chloride [Au(CN)2CL2]- is formed with φ= 0.5 x 10-4 at λirr = 254 nm. It is assumed that [Au(CN)2]- in its metal-to-ligand charge transfer state undergoes an excited state electron transfer to oxygen in the primary photochemical step.

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