scholarly journals DFT/TD-DFT Framework of Mixed-Metal Complexes with Symmetrical and Unsymmetrical Bridging Ligands—Step-By-Step Investigations: Mononuclear, Dinuclear Homometallic, and Heterometallic for Optoelectronic Applications

Materials ◽  
2021 ◽  
Vol 14 (24) ◽  
pp. 7783
Author(s):  
Dawid Zych
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Metal Complexes ◽  
Density Functional ◽  
Physical Parameters ◽  
Bridging Ligands ◽  
Functional Theory ◽  
Mixed Metal ◽  
Td Dft ◽  
Mixed Metal Complexes

Recently, mono- and dinuclear complexes have been in the interest of scientists due to their potential application in optoelectronics. Herein, progressive theoretical investigations starting from mononuclear followed by homo- and heterometallic dinuclear osmium and/or ruthenium complexes with NCN-cyclometalating bridging ligands substituted by one or two kinds of heteroaryl groups (pyrazol-1-yl and 4-(2,2-dimethylpropyloxy)pyrid-2-yl) providing the short/long axial symmetry or asymmetry are presented. Step-by-step information about the particular part that built the mixed-metal complexes is crucial to understanding their behavior and checking the necessity of their eventual studies. Evaluation by using density functional theory (DFT) calculations allowed gaining information about the frontier orbitals, energy gaps, and physical parameters of complexes and their oxidized forms. Through time-dependent density functional theory (TD-DFT), calculations showed the optical properties, with a particular emphasis on the nature of low-energy bands. The presented results are a clear indication for other scientists in the field of chemistry and materials science.

DFT Calculations on Group 5 Mixed Metal Tetramers: TaxNbyVz (x + y + z = 4)

2004 ◽  
Vol 57 (12) ◽  
pp. 1197 ◽  
Author(s):  
Magdalene A. Addicoat ◽  
Mark A. Buntine ◽  
Gregory F. Metha
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Triplet State ◽  
Density Functional ◽  
Metal Cluster ◽  
Functional Theory ◽  
Mixed Metal ◽  
Mixed Metal Cluster ◽  
Group 5

We report Density Functional Theory (DFT) calculations on mixed-metal tetramers comprised of the Group 5 (Vb) elements V, Nb, and Ta. Our results show that the lowest energy structures for Nb4 and Ta4 are regular tetrahedra with Td symmetry and singlet multiplicity whereas V4 is a triplet state with C2v symmetry. The monosubstituted isomers, A3B, all have C3v symmetry but several higher energy Cs structures have been found that are approximately 100 kJ mol−1 higher in energy. The disubstituted isomers all posses arachno-butterfly structures; the A2B2 types with C2v symmetry and the A2BC types with Cs symmetry. However, the relative openness of the arachno structures is found to be specific to the composition of the mixed-metal cluster.

scholarly journals The photochemistry of transition metal complexes using density functional theory

2013 ◽  
Vol 371 (1995) ◽  
pp. 20120134 ◽  
Author(s):  
Claudio Garino ◽  
Luca Salassa
Keyword(s):  
Density Functional Theory ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Density Functional ◽  
Organometallic Complexes ◽  
Functional Theory ◽  
Td Dft ◽  
Ru Complexes ◽  
Active Transition

The use of density functional theory (DFT) and time-dependent DFT (TD-DFT) to study the photochemistry of metal complexes is becoming increasingly important among chemists. Computational methods provide unique information on the electronic nature of excited states and their atomic structure, integrating spectroscopy observations on transient species and excited-state dynamics. In this contribution, we present an overview on photochemically active transition metal complexes investigated by DFT. In particular, we discuss a representative range of systems studied up to now, which include CO- and NO-releasing inorganic and organometallic complexes, haem and haem-like complexes dissociating small diatomic molecules, photoactive anti-cancer Pt and Ru complexes, Ru polypyridyls and diphosphino Pt derivatives.

Applications of Density Functional Theory in the Geosciences

MRS Bulletin ◽  
2006 ◽  
Vol 31 (9) ◽  
pp. 675-680 ◽  
Author(s):  
John P. Brodholt ◽  
L Voĉadlo
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Physical Parameters ◽  
Functional Theory ◽  
Mantle Minerals ◽  
High Temperature And Pressure ◽  
The Earth ◽  
Temperature And Pressure ◽  
New Phase

AbstractAlthough density functional theory (DFT) calculations have been widely used in many areas of the geosciences for the last 15 years, arguably the most successful application of these methods has been when they are used to understand the properties of minerals and melts in the Earth's pressures of the Earth's 6000 K and 360GPa) are so extreme that experiments under these conditions are very difficult. DFT calculations have been used to provide invaluable estimates of physical parameters that are fundamental to understanding the dynamics and evolution of the Earth. In particular, DFT calculations have helped provide estimates of the mineralogy and chemistry of the Earth's core, the high-temperature and pressure elasticity of the stable crystal phases in the mantle, the effect of defects on physical properties of mantle minerals, and, most recently, the discovery of a new phase of (Mg, Fe)SiO3 just above the core. These and other applications of DFT in the geosciences are described and their implications discussed.

Synthetic Route of Trithiolato-Bridged Dinuclear Arene Ruthenium(II) Complexes [(η6-P-MeC6H4Pri)2Ru2(μ2-SR)3]+

2020 ◽  
Author(s):  
Hedvika Primasova ◽  
Silviya Ninova ◽  
Ulrich Aschauer ◽  
julien Furrer ◽  
Mario de Capitani ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Metal Complexes ◽  
Density Functional ◽  
Ruthenium Complexes ◽  
Experimental Results ◽  
Dft Study ◽  
Synthetic Route ◽  
Functional Theory ◽  
Fundamental Understanding

Several dinuclear thiophenolato-bridged arene ruthenium complexes [(η6-p-MeC6H4Pri)2Ru2(μ2-SC6H4-R)3]+ could so far only<br>be obtained with moderate yields using the synthetic route established in the early 2000s. With much less reactive aliphatic<br>thiols or with bulky thiols, the reactions become even less efficient and the desired complexes are obtained with low yields<br>or not at all. We employed density functional theory (DFT) calculations to gain a fundamental understanding of the reaction<br>mechanisms leading to the formation of dithiolato and trithiolato complexes starting from the dichloro(pcymene)<br>ruthenium(II) dimer [(η6-p-MeC6H4Pri)Ru(μ2-Cl)Cl]2. The results of the DFT study enabled us to rationalise<br>experimental results and allowed us, via a modified synthetic route, to synthesise previously unreported and hitherto<br>considered as unrealistic complexes. Our study opens possibilities for the synthesis of so far inaccessible thiolato-bridged<br>dinuclear arene ruthenium(II) complexes but more generally also the synthesis of other thiolato-bridged dinuclear group 8<br>and 9 metal complexes could be reexamined.

Theoretical screening of promising donor and π-linker groups for POM-based Zn–porphyrin dyes in dye-sensitized solar cells

2019 ◽  
Vol 21 (7) ◽  
pp. 3822-3831 ◽  
Author(s):  
Yu Gao ◽  
Wei Guan ◽  
Likai Yan ◽  
Yanhong Xu
Keyword(s):  
Density Functional Theory ◽  
Solar Cells ◽  
Dft Calculations ◽  
Density Functional ◽  
Dye Sensitized Solar Cells ◽  
Time Dependent ◽  
Functional Theory ◽  
Dye Sensitized ◽  
Td Dft ◽  
Sensitized Solar Cells

A series of Zn–porphyrin dyes with different donor and π-linker groups based on the dye SM315 were systematically investigated to screen highly efficient candidates based on density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations.

Electronically excited states of cob(ii)alamin: insights from CASSCF/XMCQDPT2 and TD-DFT calculations

2016 ◽  
Vol 18 (6) ◽  
pp. 4513-4526 ◽  
Author(s):  
Brady D. Garabato ◽  
Neeraj Kumar ◽  
Piotr Lodowski ◽  
Maria Jaworska ◽  
Pawel M. Kozlowski
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Excited States ◽  
Density Functional ◽  
Time Dependent ◽  
Functional Theory ◽  
Electronically Excited States ◽  
Td Dft ◽  
Electronically Excited ◽  
Dependent Density

The low-lying excited states of cob(ii)alamin were investigated using time-dependent density functional theory (TD-DFT), and multiconfigurational CASSCF/XMCQDPT2 methodology, to help understand their role in B12-mediated reactions.

scholarly journals DFT/TD-DFT study on spectroscopic properties of zinc(II), nickel(II), and palladium(II) metal complexes with a thiourea derivative

2016 ◽  
Vol 81 (11) ◽  
pp. 1263-1272 ◽  
Author(s):  
Xin Wang ◽  
Jieqiong Li ◽  
Li Wang ◽  
Wenpeng Wu ◽  
Zheng Du ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Metal Complexes ◽  
Density Functional ◽  
Spectroscopic Properties ◽  
Tetrahedral Geometry ◽  
Functional Theory ◽  
Coordination Environment ◽  
Square Planar ◽  
Td Dft ◽  
Shoulder Peak

The geometries, electronic structures, and spectral properties of three metal complexes Zn(C10H12N3OS)2 (1), Ni(C10H12N3OS)2 (2), and Pd(C10H12N3OS)2 (3) with N-(2-pyridinyl)morpholine-4-carbothioamide as a ligand are investigated by means of DFT (density functional theory) and TD-DFT (time-dependent density functional theory) methods. Complex 1 is a distorted tetrahedral geometry, while complexes 2 and 3 present a distorted square-planar coordination environment. In the simulated range, the spectrum of complex 1 has five obvious absorption peaks and one of them has the strongest intensity. The latter two complexes have one more absorption peak and shoulder peak with the similar intensity. Moreover, the strongest peaks of complexes 2.

scholarly journals Synthetic Route of Trithiolato-Bridged Dinuclear Arene Ruthenium(II) Complexes [(η6-P-MeC6H4Pri)2Ru2(μ2-SR)3]+

2020 ◽  
Author(s):  
Hedvika Primasova ◽  
Silviya Ninova ◽  
Ulrich Aschauer ◽  
julien Furrer ◽  
Mario de Capitani ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Metal Complexes ◽  
Density Functional ◽  
Ruthenium Complexes ◽  
Experimental Results ◽  
Dft Study ◽  
Synthetic Route ◽  
Functional Theory ◽  
Fundamental Understanding

Several dinuclear thiophenolato-bridged arene ruthenium complexes [(η6-p-MeC6H4Pri)2Ru2(μ2-SC6H4-R)3]+ could so far only<br>be obtained with moderate yields using the synthetic route established in the early 2000s. With much less reactive aliphatic<br>thiols or with bulky thiols, the reactions become even less efficient and the desired complexes are obtained with low yields<br>or not at all. We employed density functional theory (DFT) calculations to gain a fundamental understanding of the reaction<br>mechanisms leading to the formation of dithiolato and trithiolato complexes starting from the dichloro(pcymene)<br>ruthenium(II) dimer [(η6-p-MeC6H4Pri)Ru(μ2-Cl)Cl]2. The results of the DFT study enabled us to rationalise<br>experimental results and allowed us, via a modified synthetic route, to synthesise previously unreported and hitherto<br>considered as unrealistic complexes. Our study opens possibilities for the synthesis of so far inaccessible thiolato-bridged<br>dinuclear arene ruthenium(II) complexes but more generally also the synthesis of other thiolato-bridged dinuclear group 8<br>and 9 metal complexes could be reexamined.

scholarly journals Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

2016 ◽  
Vol 12 ◽  
pp. 117-124 ◽  
Author(s):  
Albert Poater
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Dinuclear Complex ◽  
Rhodium Complexes ◽  
Geometrical Isomers ◽  
Bridging Ligands ◽  
Functional Theory

Bearing the versatility of N-heterocyclic carbene (NHC) ligands, here density functional theory (DFT) calculations unravel the capacity of coordination of a deprotonated NHC ligand (pNHC) to generate a doubly C2,N3-bridged dinuclear complex. Here, in particular the discussion is based on the combination of the deprotonated 1-arylimidazol (aryl = mesityl (Mes)) with [M(cod)(μ-Cl)] (M = Ir, Rh) generated two geometrical isomers of complex [M(cod){µ-C3H2N2(Mes)-κC2,κN3}]2). The latter two isomers display conformations head-to-head (H-H) and head-to-tail (H-T) of C S and C 2 symmetry, respectively. The isomerization from the H-H to the H-T conformation is feasible, whereas next substitutions of the cod ligand by CO first, and PMe3 later confirm the H-T coordination as the thermodynamically preferred. It is envisaged the exchange of the metal, from iridium to rhodium, confirming here the innocence of the nature of the metal for such arrangements of the bridging ligands.

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