Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles

Alemayehu, Abraham B.; Vázquez‐Lima, Hugo; McCormick, Laura J.; Ghosh, Abhik

doi:10.1039/c7cc01549f

Cited by 25 publications

(31 citation statements)

References 32 publications

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“…The terminal oxo ligand affords a high inertness at the opposite axial position ( Nigel-Etinger et al., 2013 )( Schweyen et al., 2017 ). To the best of our knowledge, all attempted efforts for the isolation of molybdenum(III) corroles were not successful ( Alemayehu et al., 2017 ; Buckley and Arnold, 2015 ).…”

Section: Introductionmentioning

confidence: 99%

Hydrogen evolution catalysis by terminal molybdenum-oxo complexes

et al. 2021

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Summary Stable complexes with terminal triply bound metal-oxygen bonds are usually not considered as valuable catalysts for the hydrogen evolution reaction (HER). We now report the preparation of three conceptually different (oxo)molybdenum(V) corroles for testing if proton-assisted 2-electron reduction will lead to hyper-reactive molybdenum(III) capable of converting protons to hydrogen gas. The upto 670 mV differences in the [(oxo)Mo(IV)] - /[(oxo)Mo(III)] −2 redox potentials of the dissolved complexes came into effect by the catalytic onset potential for proton reduction thereby, significantly earlier than their reduction process in the absence of acids, but the two more promising complexes were not stable at practical conditions. Under heterogeneous conditions, the smallest and most electron-withdrawing catalyst did excel by all relevant criteria, including a 97% Faradaic efficiency for catalyzing HER from acidic water. This suggests complexes based on molybdenum, the only sustainable heavy transition metal, as catalysts for other yet unexplored green-energy-relevant processes.

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Section: Introductionmentioning

confidence: 99%

Hydrogen evolution catalysis by terminal molybdenum-oxo complexes

et al. 2021

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“…We must also not forget that the FeMo-co molecular system contains an atom of the element molybdenum, which is heavy enough to merit treatment with relativistic methods or pseudopotentials in studies of inorganic complexes [85][86][87] and enzymes. 88 In particular, relativistic calculations have been already used in FeMo-co research.…”

Section: Comment On Quantum Advantage In Femo-co Researchmentioning

confidence: 99%

How will quantum computers provide an industrially relevant computational advantage in quantum chemistry?

Elfving¹,

Broer²,

Webber³

et al. 2020

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Numerous reports claim that quantum advantage, which should emerge as a direct consequence of the advent of quantum computers, will herald a new era of chemical research because it will enable scientists to perform the kinds of quantum chemical simulations that have not been possible before. Such simulations on quantum computers, promising a significantly greater accuracy and speed, are projected to exert a great impact on the way we can probe reality, predict the outcomes of chemical experiments, and even drive design of drugs, catalysts, and materials. In this work we review the current status of quantum hardware and algorithm theory and examine whether such popular claims about quantum advantage are really going to be transformative. We go over subtle complications of quantum chemical research that tend to be overlooked in discussions involving quantum computers. We estimate quantum computer resources that will be required for performing calculations on quantum computers with chemical accuracy for several types of molecules. In particular, we directly compare the resources and timings associated with classical and quantum computers for the molecules H2 for increasing basis set sizes, and Cr2 for a variety of complete active spaces (CAS) within the scope of the CASCI and CASSCF methods. The results obtained for the chromium dimer enable us to estimate the size of the active space at which computations of non-dynamic correlation on a quantum computer should take less time than analogous computations on a classical computer. The transition point should occur at around 19 ≤ N ≤ 34, for CAS of the type (N, N ), under the assumption of the much-researched surface code. This is significantly smaller than the active spaces discussed in the context of quantum advantage in prior publications. Using this result, we speculate on the types of chemical applications for which the use of quantum computers would be both beneficial and relevant to industrial applications in the short term.

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“…The 'acetate method' has since become the method of choice for the synthesis of Au corroles. Understandably, we were intrigued by the possibility of inserting other heavier transition metals into corroles and, to our satisfaction, the rst 99 TcO, 8 ReO, 9 ReNAr, 10 RuN, 11 OsN, 12 and Pt 13,14 triarylcorroles (as well as Mo and W biscorroles [15][16][17] and quadruple-bonded Re corrole dimers 18 ) were synthesized in our Tromsø laboratory. Several of the 5d metallocorroles [19][20][21][22][23][24] were found to exhibit room-temperature NIR phosphorescence, leading to applications as oxygen sensors and as photosensitizers in photodynamic therapy and dye-sensitized solar cells.…”

Section: Introductionmentioning

confidence: 99%