Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

Chmela, Jiří; Harding, Michael E.; Matioszek, Dimitri; Anson, Christopher E.; Breher, Frank; Klopper, Wim

doi:10.1002/cphc.201500626

Cited by 19 publications

(32 citation statements)

References 90 publications

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“…Furthermore, the BSE approach may outperform the TDDFT approach for states with multiple‐excitation or charge‐transfer character, as for example occurring in transition‐metal complexes. It remains to be seen whether the BSE approach could be a useful tool for the study of cooperative effects in electronic spectra of oligonuclear transition‐metal complexes …”

Section: Resultsmentioning

confidence: 99%

Implementation of the Bethe−Salpeter equation in the TURBOMOLE program

2016

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A software update solving the Bethe-Salpeter equation (BSE) is reported for the ESCF module of the TURBOMOLE program for the theoretical description of electronically excited states of atoms and molecules. A resolution-of-the-identity (RI) approximation is used for all two-electron electron-repulsion integrals that are required for solving the equation. Symmetry is utilized for the point group D and its subgroups, and the BSE approach can be applied in either a spin-restricted or a spin-unrestricted Kohn-Sham formalism. Triplet as well as singlet excited states of closed-shell atoms and molecules can be treated in the spin-restricted formalism. As a side product, the present software update also allows for the application of the RI approximation to the Hartree-Fock exchange contribution that occurs when a hybrid functional is used in time-dependent density-functional theory. © 2016 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

Implementation of the Bethe−Salpeter equation in the TURBOMOLE program

2016

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“…Recent reports demonstrated the measurement of cooperativity for the simpler systems at the molecular level could be achieved by energy consideration. [12,13] Therefore, the measurement of interaction energies of the entire system with respect to the interaction energies between all individual subsystems will allow determination of cooperativity for a system in which no chemical transformations occur. For the systems where chemical transformations occur, the cooperativity can be measured by considering the energy of activation in the synergistic system Between 2012 and 2019, he was a W2-Proffesor at the Freie Universität Berlin.…”

Section: Introductionmentioning

confidence: 99%

Cooperative Effects in Multimetallic Complexes Applied in Catalysis

et al. 2021

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The field of multimetallic catalysis is rapidly developing and some multimetallic complexes catalyze organic transformations to yield the desired products in more efficient ways owing to the combined action of different metals in a cooperative fashion. This Concept article describes the recent advances of cooperative catalysis playing in multimetallic systems such as homo-multimetallic complexes with short metal-metal distances, homo-multimetallic complexes with long metal-metal distances, hetero-multimetallic complexes and metallocenebased multimetallic complexes with special attention towards redox-switchable catalysis. Examples are illustrated in which the use of multimetallic complexes show clear enhancement of catalytic outcomes when compared with the sum of their corresponding mononuclear counterparts. Furthermore, several examples are discussed showing the effects of electronic communication in cooperative systems.

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“…Furthermore, quantum chemical calculations on the electronic communication in the heterobimetallic complexes are provided. We are particularly interested in polynuclear complexes of this type as a means to explore cooperative effects between metal centers …”

Section: Introductionmentioning

confidence: 99%

“…We are particularly interested in polynuclear complexes of this type as ameans to explore cooperative effects between metal centers. [28,29]…”

Section: Introductionmentioning

confidence: 99%

A Redox‐Switchable Germylene and its Ligating Properties in Selected Transition Metal Complexes

Walz

Moos

Garnier

et al. 2016

Chemistry A European J

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The synthesis, structure, and full characterization of a redox-switchable germylene based on a [3]ferrocenophane ligand arrangement, [Fc(NMes) Ge] (4), is presented. The mesityl (Mes)-substituted title compound is readily available from Fc(NHMes) (2) and Ge{N(SiMe ) } , or from the dilithiated, highly air- and moisture-sensitive compound Fc(NLiMes) ⋅3 Et O (3) and GeCl . Cyclic voltammetry studies are provided for 4, confirming the above-mentioned view of a redox-switchable germylene metalloligand. Although several 1:1 Rh and Ir complexes of 4 (5-7) are cleanly formed in solution, all attempts to isolate them in pure form failed due to stability problems. However, crystalline solids of [Mo(κ Ge-4) (CO) ] (8) and [W(κ Ge-4) (CO) ] (9) were isolated and fully characterized by common spectroscopic techniques (8 by X-ray diffraction). DFT calculations were performed on a series of model compounds to elucidate a conceivable interplay between the metal atoms in neutral and cationic bimetallic complexes of the type [Rh(κ E-qE)(CO) Cl] (qE=[Fc(NPh) E] with E=C, Si, Ge). The bonding characteristics of the coordinated Fc-based metalloligands (qE/qE ) are strongly affected upon in silico oxidation of the calculated complexes. The calculated Tolman electronic parameter (TEP) significantly increases by approximately 20 cm (E=C) to 25 cm (E=Si, Ge) upon oxidation. The change in the ligand-donating abilities upon oxidation can mainly be attributed to Coulombic effects, whereas an orbital-based interaction appears to have only a minor influence.

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Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

Cited by 19 publications

References 90 publications

Implementation of the Bethe−Salpeter equation in the TURBOMOLE program

Implementation of the Bethe−Salpeter equation in the TURBOMOLE program

Cooperative Effects in Multimetallic Complexes Applied in Catalysis

A Redox‐Switchable Germylene and its Ligating Properties in Selected Transition Metal Complexes

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