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Our research deals with the application of computational chemistry methods to a variety of topics, in most cases in close collaboration with experimental groups at ICIQ and at other institutions. These topics fall into three main categories:
  • Structure and reactivity of organometallic compounds and homogeneous catalysis related issues: characterization in-silico of reactive intermediates, elucidation of reaction mechanisms, origin of the chemo-, regio- and enantioselectivity, ligand effects, ligand design and structure-selectivity relationships.
  • Polyoxometalates: electronic structure, mechanism of catalytic oxidation reactions, dynamic structure of cations and solvent water molecules around and inside POMs.
  • Supramolecular chemistry: structure of host-guest systems, assessment of non-bonding interactions and supramolecular catalysis.

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Alkali-Driven Disassembly and Reassembly of Molecular Niobium Oxide in Water DOI: 10.19061/iochem-bd-1-88

Alkali counterions for polyoxometalate (POM) clusters control solubility with distinct periodic trends, but evidence for alkali control over speciation is ambiguous. Here we show that a simple Nb-POM, [Nb10O28]6– ({Nb10}), converts to oligomers of (HxNb24O72)(24–x)– ({Nb24}) upon adding only alkali chloride salts, even in buffered neutral solutions.

This dataset derived results are published in:

Manuscript title: Alkali-Driven Disassembly and Reassembly of Molecular Niobium Oxide in Water

Journal: J. Am. Chem. Soc.

DOI: 10.1021/jacs.8b05015

Al(x)Cr(y)_Keggin_oxos DOI: 10.19061/iochem-bd-1-23

This dataset derived results are published in:

Manuscript title: Crystallizing Elusive Chromium Polycations.

Journal: Chem

DOI: 10.1016/j.chempr.2016.11.006

A Metal-Free Synthesis of N-Aryl Carbamates under Ambient Conditions DOI: 10.19061/iochem-bd-1-3

This dataset derived results are published in:

Manuscript title: A Metal-Free Synthesis of N-Aryl Carbamates under Ambient Conditions

Journal: Angew. Chem. Int. Ed.

DOI: 10.1002/anie.201504956

Analysis of the interaction between Keplerate nanocapsules and their anionic ligands DOI: 10.19061/iochem-bd-1-33

This dataset derived results are published in:

Manuscript title: Anions coordinating anions: Analysis of the interaction between anionic Keplerate nanocapsules and their anionic ligands

Journal: PCCP

DOI: 10.1039/C6CP08511C

AnS2(2+)_cations DOI: 10.19061/iochem-bd-1-30

Actinide disulphide dications, AnS22+, were produced in the gas phase for An = Th and Np by reaction of An2+ cations with the sulfur-atom donor COS, in a sequential abstraction process of two sulfur atoms, as examined by FTICR mass spectrometry. For An = Pu and Am, An2+ ions were unreactive with COS and did not yield any sulphide species. High level multiconfigurational (CASPT2) calculations were performed to assess the structures and bonding of the new AnS22+ species obtained for An = Th, Np, as well as for An = Pu to examine trends along the An series, and for An = U to compare with a previous experimental study and DFT computational scrutiny of US22+. The CASPT2 results showed that, like in the case of uranium, the new AnS22+ ions have ground states with triangular geometries, corresponding to the presence of a persulphide in the case of thorium that formally leads to a stable ThIVS22+ species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a AnIIIS22+ species. The computations also revealed that linear thioactinyl structures are higher in energy, with a difference that increases fourfold upon moving from U to Pu, apparently indicating that it will be even more pronounced for Am.

This dataset derived results are published in:

Manuscript title: Synthesis, structure and bonding of actinide disulphide dications in the gas phase

Journal: PCCP

DOI: 10.1039/c7cp01446e

Aromatic_Amination_of_Lactones DOI: 10.19061/iochem-bd-1-21

This dataset derived results are published in:

Manuscript title: Metal-Free Synthesis of N-Aryl Amides using Organocatalytic Ring-Opening Aminolysis of Lactones

Journal: ChemSusChem

DOI: 10.1002/cssc.201700415

Br catalyzed propylene carbonate formation DOI: 10.19061/iochem-bd-1-132

Static calculations (PM6, PM7 and M06-2X) for Br-catalyzed carbon dioxide fixation from propylene oxide to propylene carbonate.

No other publication derived

Cs+ contac ion-pairing between hexaniobates and hexatantalates DOI: 10.19061/iochem-bd-1-31

Computational studies ascertained more persistent Cs+–[Ta6O19] ion pairs than Cs+–[Nb6O19] ion pairs, and bond energy decomposition analyses determined relativistic effects to be the differentiating factor between the two. These distinctions are likely responsible for many of the unexplained differences between aqueous Nb and Ta chemistry, while they are so similar in the solid state.

This dataset derived results are published in:

Manuscript title: Cs+ contac ion-pairing between hexaniobates and hexatantalates

Journal: PCCP

DOI: 10.1039/C6CP08454K

Deciphering key intermediates DOI: 10.19061/iochem-bd-1-58

The identification of catalytic intermediates in the conversion of carbon dioxide is vital for improved catalyst design and optimization of structure–reactivity relationships, but remains elusive. Here, we report that intermolecular hydrogen bonding interactions between an epoxy alcohol, water and the catalyst structure are crucial towards the formation of a cyclic carbonate from carbon dioxide. A combination of multiple in situ and ex situ techniques including substrate labelling, kinetic studies, computational analysis, operando infrared spectroscopy and X-ray diffraction was applied to identify and support the structural connectivities of several previously unknown intermediates. An epoxy alcohol–water cluster formed by hydrogen bonding was identified as the initial intermediate able to trap CO2 and an elusive alkyl carbonate anion was also detected. The synergistic spectroscopic and computational analysis shown here offers a unique insight under operando conditions, as well as a useful analytical blueprint for key suggested intermediates in other mechanistically related CO2 conversion processes.

This dataset derived results are published in:

Manuscript title: Deciphering key intermediates in the transformation of carbon dioxide into heterocyclic products

Journal: Nature Catalysis

Disorder

No other publication derived

Electronic Structure Studies on the Whole Keplerate Family DOI: 10.19061/iochem-bd-1-24

A comprehensive study on the electronic structure of nano-scale molecular oxide capsules of the type [{MVI(MVI)5O21}12{M'V2O2(μ-X)(μ-Y)(Ln- )}30](12+n)-, where M,M'=Mo,W, and the bridging ligands X,Y=O,S, carried out by means of density functional theory based methods.

This dataset derived results are published in:

Manuscript title: Electronic Structure Studies on the Whole Keplerate Family: Predicting New Members

Journal: Chem. Eur. J.

DOI: 10.1002/chem.201605981

Evaluation of the Catalytic Activity DOI: 10.19061/iochem-bd-1-110

The reaction mechanism for formation of cyclic carbonates from CO2 and 1,2-epoxyhexane catalyzed by the [Al(amino-triphenolate)]/NBu4I binary system has been investigated by using Density Functional Theory (DFT) based methods. A monometallic mechanism is proposed and the main steps of the reaction are described in detail. The energetic span model (δE) was used to theoretically determine the turnover frequencies (TOFs) of the catalytic cycle and to evaluate the efficiency of the aluminum complex in mediating the CO2 addition reaction. Our findings indicate that entropy changes in solution must be included in order to compute TOF values in line with the experimental results.

This dataset derived results are published in:

Manuscript title: Entropic corrections for the evaluation of the catalytic activity in the Al(III) catalysed formation of cyclic carbonates from CO2 and epoxides

Journal: Catal. Sci. Technol.

DOI: 10.1039/c9cy01285k

Favourable_Martin DOI: 10.19061/iochem-bd-1-129

No other publication derived

Fe(III) Keggin structures DOI: 10.19061/iochem-bd-1-18

This dataset derived results are published in:

Manuscript title: Magneto-Structural Analysis of Iron(III) Keggin Polyoxometalates

Journal: J. Phys. Chem. A

DOI: 10.1021/acs.jpca.6b10763

Hierarchical self-assembly of polyoxometalate-based hybrids driven by metal coordination and electrostatic interactions: from discrete supramolecular species to dense monodisperse nanoparticles. DOI: 10.19061/iochem-bd-1-5

This dataset derived results are published in:

Manuscript title: Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Species to Dense Monodisperse Nanoparticles

Journal: J. Am. Chem. Soc.

DOI: 10.1021/jacs.6b00972

Hosoya_Reaction DOI: 10.19061/iochem-bd-1-134

No other publication derived

Hydrogen_Evolution_Catalysis DOI: 10.19061/iochem-bd-1-99

This dataset derived results are published in:

Manuscript title: Tuning and mechanistic insights of metal chalcogenide molecular catalysts for the hydrogen-evolution reaction

Journal: Nat. Commun.

DOI: 10.1038/s41467-018-08208-4

Master Thesis

No other publication derived

Mechanistic Insights into the Carbon Dioxide-Cyclohexene Oxide Copolymerization reaction DOI: 10.19061/iochem-bd-1-17

A detailed study on the mechanism for the alternating copolymerization of cyclohexene oxide (CHO) and CO2 mediated by a [Al{amino‐tri(phenolate)}]/NBu4I binary catalyst system has been carried out using density functional theory (DFT) based methods.

This dataset derived results are published in:

Manuscript title: Mechanistic Insights into the Carbon Dioxide-Cyclohexene Oxide Copolymerization reaction: Is one Metal Center enough?

Journal: ChemSusChem

DOI: 10.1002/cssc.20160152

Mechanistic Study on Limonene Oxide and Carbon Dioxide Copolymerisation

This dataset derived results are published in:

Manuscript title: AlIII-Catalysed Formation of Poly(limonene)carbonate: DFT Analysis of the Origin of Stereoregularity

Journal: Chem. Eur. J.

DOI: 10.1002/chem.201406334

Mo(I)_hydrogen_generation

No other publication derived

Molecular basis for the recognition of higher fullerenes into ureidopyrimidinonecyclotriveratrylene self-assembled capsules DOI: 10.19061/iochem-bd-1-7

This dataset derived results are published in:

Manuscript title: Molecular Basis for the Recognition of Higher Fullerenes into Ureidopyrimidinone–Cyclotriveratrylene Self-Assembled Capsules

Journal: Chem. Eur. J.

DOI: 10.1002/chem.201601690

Molecular Motion and Conformational Interconversion of IrI·COD Included in Rebek’s Self-Folding Octaamide Cavitand DOI: 10.19061/iochem-bd-1-2

This dataset derived results are published in:

Manuscript title: Molecular Motion and Conformational Interconversion of IrI·COD Included in Rebek’s Self-Folding Octaamide Cavitand

Journal: J. Am. Chem. Soc.

DOI: 10.1021/jacs.5b12646

out

No other publication derived

Oxidative Carbon-Carbon Bond Cleavage by Vanadium Catalyst DOI: 10.19061/iochem-bd-1-53

The aerobic oxidative CC bond cleavage of vicinal diols catalyzed by vanadium aminotriphenolates is described. Our results show that CC bond cleavag e can be performed in different solvents,under an air or oxygen atmosphere, with a large variety of glycols (cyclic or linear, with aromati c or aliphaticsubstituents) affording the corresponding carbonyl derivatives with high chemoselectivity.Reactions can be performed with as little as 10 ppm of catalyst reaching TON up to 81,000 and TOFs of up to4150 h1. A reaction mechanism, rationalized by de nsity functional theory calculations, is also proposed.

This dataset derived results are published in:

Manuscript title: Efficient Vanadium-Catalyzed Aerobic CC Bond OxidativeCleavage of Vicinal Diols

Journal: Adv. Synth. Catal.

DOI: https://doi.org/10.1002/adsc.201800050

Paper_Calculations

No other publication derived

Paper_Calculations DOI: 10.19061/iochem-bd-1-117

No other publication derived

Photochromism and Dual-Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch DOI: 10.19061/iochem-bd-1-27

This dataset derived results are published in:

Manuscript title: Photochromism and Dual-Color Fluorescence in a Polyoxometalate–Benzospiropyran Molecular Switch

Journal: Angew. Chem. Int. Ed.

POMS DOI: 10.19061/iochem-bd-1-60

No other publication derived

POMsDB DOI: 10.19061/iochem-bd-1-128

This is POMsDB, a polyoxometalates (POMs) database which collects computational data on a growing list of POMs: optimized geometries, vibrational frequencies, atomic charges, molecular orbital energies, etc... Some data was combined to create all necessary files to run classical molecular dynamics simulations with GROMACS and NAMD.

Each POM contains downloadable content, such as outputs and a compressed file with the molecular dynamics files in ZIP format. The force field is designed to simulations where the geometry of the POM is frozen.

Polyoxometalates list:
- Lindqvist: [M₆O₁₉]n- (M=W, n=2; M=Nb, n=8)
- Anderson: [M₇O₂₄]n- (M=W,Mo, n=6)
- Keggin (alpha, beta, gamma, delta, epsilon): [XM₁₂O₄₀]n- (X=P, M=W,Mo, n=3)
- Wells-Dawson: [X₂M₁₈O₆₂]n- (X=P, M=W,Mo, n=6)
- Preyssler: [X₅M₃₀O₁₁₀]n- (X=P, M=W, n=15)
POMsDB
Computational Details:
- ADF 2018 package(1-3): GGA density functional of Becke and Perdew (BP86)(4). Slater-type basis set of triple-Z with polarization (TZP)(6). Zeroth-Order Regular Approximation (ZORA)(7-9) formalism included. Solvent effects incorporated with the conductor-like screening model (COSMO). Quadrupolar derived charges analysis(11) used for atomic charge calculation.
- Gaussian 16 package(12): GGA density functional of Becke and Perdew (BP86)(4-5). Gaussian-type basis set of double-Z with ECP (LANL2DZ)(13-16). Solvent effects incorporated self-consistently using the Polarizable Continuum Model (PCM)(17). CHelpG charge analysis(18) used for atomic charge calculation. CHelphG charges were obtained using crystallografic and ionic radii related by Shannon and Van Horn(19,20).
- Files for molecular dynamics simulations are generated with Poly_type(21).

Authors:
- Albert Masip[1], Mireia Segado[2], Carles Bo[1],[2]
[1] Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Carrer Marcel·li Domingo, s/n, 43007 Tarragona, Spain
[2] Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avgda. Països Catalans 16, 43007 Tarragona, Spain

Citation:
Masip, A.; Segado, M.; Bo, C.; DOI: 10.19061/iochem-bd-1-128

References:
(1) G.te Velde, F.M. Bickelhaupt, E.J. Baerends, C. Fonseca Guerra, S.J.A. van Gisbergen, J.G. Snijders and T. Ziegler, Chemistry with ADF, Journal of Computational Chemistry 22, 931 (2001)
(2) C.Fonseca Guerra, J.G. Snijders, G. te Velde and E.J. Baerends, Towards an order-N DFT method, Theoretical Chemistry Accounts 99, 391 (1998)
(3) ADF2018, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com.
(4) A.D. Becke, Density-functional exchange-energy approximation with correct asymptotic behavior, Physical Review A 38, 3098 (1988)
(5) J.P. Perdew, Density-functional approximation for the correlation energy of the inhomogeneous electron gas, Physical Revied B 33, 8822 (1986) Erratum: J.P. Perdew, Physical Review B 34, 7406 (1986)
(6) E. van Lenthe and E.J. Baerends, Optimized Slater-type basis sets for the elements 1-118, Journal of Computational Chemistry 24, 1142 (2003)
(7) E. van Lenthe, E.J. Baerends and J.G. Snijders, Relativistic regular two-component Hamiltonians, Journal of Chemical Physics 99, 4597 (1993)
(8) E. van Lenthe, E.J. Baerends and J.G. Snijders, Relativistic total energy using regular approximations, Journal of Chemical Physics 101, 9783 (1994)
(9) E. van Lenthe, A.E. Ehlers and E.J. Baerends, Geometry optimization in the Zero Order Regular Approximation for relativistic effects, Journal of Chemical Physics 110, 8943 (1999)
(10) C.C. Pye and T. Ziegler, An implementation of the conductor-like screening model of solvation within the Amsterdam density functional package, Theoretical Chemistry Accounts 101, 396 (1999)
(11) M. Swart, P.Th. van Duijnen and J.G. Snijders, A charge analysis derived from an atomic multipole expansion, Journal of Computational Chemistry 22, 79 (2001)
(12) Gaussian 16, Revision A.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2016.
(13) T. H. Dunning Jr. and P. J. Hay, in Modern Theoretical Chemistry, Ed. H. F. Schaefer III, Vol. 3 (Plenum, New York, 1977) 1-28.
(14) P. J. Hay and W. R. Wadt, “Ab initio effective core potentials for molecular calculations – potentials for the transition-metal atoms Sc to Hg,” J. Chem. Phys., 82 (1985) 270-83. DOI: 10.1063/1.448799
(15) W. R. Wadt and P. J. Hay, “Ab initio effective core potentials for molecular calculations – potentials for main group elements Na to Bi,” J. Chem. Phys., 82 (1985) 284-98. DOI: 10.1063/1.448800
(16) P. J. Hay and W. R. Wadt, “Ab initio effective core potentials for molecular calculations – potentials for K to Au including the outermost core orbitals,” J. Chem. Phys., 82 (1985) 299-310. DOI: 10.1063/1.448975
(17) G. Scalmani and M. J. Frisch, “Continuous surface charge polarizable continuum models of solvation. I. General formalism,” J. Chem. Phys., 132 (2010) 114110 DOI: 10.1063/1.3359469
(18) C. M. Breneman and K. B. Wiberg, “Determining atom-centered monopoles from molecular electrostatic potentials – the need for high sampling density in formamide conformational-analysis,” J. Comp. Chem., 11 (1990) 361-73. DOI: 10.1002/jcc.540110311
(19) R. D. Shannon, Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst. A32, 751-767 (1976).
(20) J. David Van Horn, Electronic Table of Shannon Ionic Radii, 2001, downloaded 05/29/2019.
(21) Poly_type. Carles Bo. ICIQ. 2019

No other publication derived

PrLn DOI: 10.19061/iochem-bd-1-64

No other publication derived

Raman spectra of species observed during the formation of [Mo 132] Keplerates DOI: 10.19061/iochem-bd-1-32

Infrared and Raman Spectra of MoxOy species

This dataset derived results are published in:

Manuscript title: Direct Observation of the Formation Pathway of [Mo 132] Keplerates

Journal: Inorg. Chem.

DOI: 10.1021/acs.inorgchem.5b02570

Regioselective Catalysis by the {Mo132} nanocapsule DOI: 10.19061/iochem-bd-1-54

This dataset derived results are published in:

Manuscript title: Regioselective Catalysis by the {Mo132} nanocapsule: A computational inspection.

Journal: Eur. J. Inorg. Chem.

DOI: 10.1002/ejic.201800155

Strategic capture of the {Nb7} polyoxometalate DOI: 10.19061/iochem-bd-1-125

Find a collection of 27 DFT optimized geometries.
1) A set of 9 isomers of the {Nb14} disordered with -yl oxo and/or peroxo groups.
2) A set of 14 isomers of the {Nb23}2 disordered with {Nb} and/or {U} atoms.
3) The 4 structures left correspond to the isodesmic pair molecules.

This dataset derived results are published in:

Manuscript title: Strategic capture of the {Nb7} polyoxometalate

Journal: Chem. Eur. J.

DOI: 10.1002/chem.201902770

Thermodynamic Stability of Heterodimetallic [LnLn’] Complexes DOI: 10.19061/iochem-bd-1-22

The solid state and solution configuration of the heterodimetallic complexes, (Hpy)[CeEr(HL)3(NO3)(py)(H2O)] (1), (Hpy)[PrSm(HL)3(NO3)(py)(H2O)] (2) and (Hpy)2[LaYb(HL)3(NO3)(H2O)](NO3) (3), where H3L is 6-(3-oxo-3-(2-hydroxyphenyl)propionyl)pyridine-2-carboxylic acid, are analysed experimentally and through DFT calculations. The theoretical study is also extended to the [LaCe], [LaLu] and [CeGd] analogues. The results are consistent with a remarkable selectivity of the metal distribution within the molecule while in the solid state, enhanced by the size difference of both metals. This selectivity is significantly reduced in solution.

This dataset derived results are published in:

Manuscript title: Thermodynamic Stability of Heterodimetallic [LnLn’] Complexes: Synthesis and DFT Studies

DOI: 10.1002/chem.201700095

Yorimitsu_reaction DOI: 10.19061/iochem-bd-1-126

No other publication derived

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