Tunning the optical properties of a photocatalytic metal-organic framework by means of molecular modelling

Simple item page
datacite.alternateIdentifier.citationNew Journal of Chemistry, 47 (7), 3444-3430, 2023
datacite.alternateIdentifier.doi10.1039/d2nj04532j
datacite.alternateIdentifier.issn1369-9261
datacite.creatorTreto-Suárez, Manuel Alejandro
datacite.creatorHidalgo-Rosa, Yoan
datacite.creatorUlecia, Karel Mena
datacite.creatorPáez-Hernández, Dayán
datacite.creatorKoivisto, Bryan D.
datacite.creatorZárate, Ximena P.
datacite.creatorSchott V, Eduardo
datacite.date2023
datacite.rightsRegistro bibliográfico
datacite.subjectNitrogen Dioxide
datacite.subjectTitanium
datacite.subjectCharge Transfer
datacite.subjectComplexation
datacite.subjectComputational Chemistry
datacite.subjectDensity Functional Theory
datacite.subjectDesign For Testability
datacite.subjectExcited States
datacite.subjectHydrogen Bonds
datacite.subjectLigands
datacite.subjectLight Absorption
datacite.subjectMolecular Orbitals
datacite.subjectNitrogen Oxides
datacite.subjectOrganic Polymers
datacite.subjectOrganometallics
datacite.subjectPhotocatalytic Activity
datacite.subjectComplete Active Space Self Consistent Fields
datacite.subjectComplete Active Space Self-consistent Fields
datacite.subjectConversion Rates
datacite.subjectDicarboxylates
datacite.subjectIsostructural
datacite.subjectLocalised
datacite.subjectMetalorganic Frameworks (mofs)
datacite.subjectPhoto-catalytic
datacite.subjectRational Design
datacite.subjectTheoretical Study
datacite.subjectOptical Properties
datacite.subject1,4 Benzenedicarboxylate
datacite.subjectAmine
datacite.subjectBenzene Derivative
datacite.subjectCarboxylic Acid Derivative
datacite.subjectFunctional Group
datacite.subjectHydroxyl Group
datacite.subjectMetal Complex
datacite.subjectMetal Organic Framework
datacite.subjectMethyl Group
datacite.subjectNitrogen Dioxide
datacite.subjectTitanium
datacite.subjectUnclassified Drug
datacite.subjectAbsorption Spectroscopy
datacite.subjectArticle
datacite.subjectChemical Interaction
datacite.subjectChemical Structure
datacite.subjectControlled Study
datacite.subjectDecomposition
datacite.subjectDensity Functional Theory
datacite.subjectElectron Transport
datacite.subjectLight Absorption
datacite.subjectMolecular Model
datacite.subjectMolecular Stability
datacite.subjectOptics
datacite.subjectPhotocatalysis
datacite.subjectStatic Electricity
datacite.subjectStructure Analysis
datacite.subjectSubstitution Reaction
datacite.subjectTheoretical Study
datacite.subjectTime Dependent Density Functional Theory
datacite.subjectUltraviolet Visible Spectroscopy
datacite.subjectValence (chemistry)
datacite.titleTunning the optical properties of a photocatalytic metal-organic framework by means of molecular modelling
dc.contributor.authorMENA ULECIA, KAREL
dc.date.accessioned2025-10-06T14:22:01Z
dc.date.available2025-10-06T14:22:01Z
dc.description.abstractA theoretical study of reported isostructural metal-organic frameworks (MOFs) based on MIL-125-Ti4+ was performed to understand the optical properties and facilitate the rational design of new materials with potentially improved features as photocatalysts. The experimentally tested MOFs (MIL-125-Ti4+ labeled as M) were functionalized with -NH<inf>2</inf>, -CH<inf>3</inf>, and -OH substituents on the 1,4-benzene-dicarboxylate (BDC) linker (labeled as M-NH2, M-CH3, and M-OH, respectively), generating a broadened light-harvesting of the MOF and an improvement of the N<inf>2</inf> conversion rate. The M-NH2 showed the highest visible light absorption and N<inf>2</inf> photocatalysis efficiency experimentally. This substituent effect was theoretically studied via Density Functional Theory (DFT) calculations on the ground singlet (S<inf>0</inf>) and first excited state (singlet and triplet) using Time-Dependent Density Functional Theory (TD-DFT), the Morokuma-Ziegler energy decomposition scheme, and Natural Orbital of Chemical Valence (NOCV) analysis. These tools allowed for the reproduction of the optical properties and performance in good agreement with the experiment and highlight that the N<inf>2</inf> conversion rate increases as the donor character of the R group improve. This effect is a result of the stabilization of the Occupied Molecular Orbitals (localized on the BDC linker), a decrease in the charge recombination, and by an increase of charge flow to the metal center favoring the photocatalytic Ti4+/Ti3+ reduction (via ligand to metal charge transfer (LMCT) transition). These systems also display a metal-ligand charge transfer (MLCT) process in the excited state favoring the emission localized in the BDC linker, which was confirmed via Complete Active Space Self-Consistent Field (CASSCF) calculation. Finally, through CASSCF, it was possible to propose two new isoreticular structures, with the -SH and -NO<inf>2</inf> substituents (labeled as M-SH and M-NO2), with the -SH variant exhibiting optical and photocatalytic properties that could rival M with -NH<inf>2</inf> substitution. © 2023 Elsevier B.V., All rights reserved.
dc.description.ia_keywordmetal, optical, properties, charge, labeled, linker, photocatalytic
dc.identifier.issn1144-0546
dc.identifier.urihttps://repositoriodigital.uct.cl/handle/10925/6908
dc.language.isoen
dc.publisherRoyal Society Of Chemistry
dc.relationinstname: ANID
dc.relationreponame: Repositorio Digital RI2.0
dc.rights.driverinfo:eu-repo/semantics/openAccess
dc.sourceNew Journal of Chemistry
dc.subject.ia_odsODS 7: Energía asequible y no contaminante
dc.subject.ia_oecd1nCiencias Naturales
dc.subject.ia_oecd2nCiencias Físicas
dc.subject.ia_oecd3nQuímica
dc.type.driverinfo:eu-repo/semantics/article
dc.type.driverhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.type.openaireinfo:eu-repo/semantics/publishedVersion
dspace.entity.typePublication
oaire.citationEdition2023
oaire.citationEndPage3444
oaire.citationIssue7
oaire.citationStartPage3430
oaire.citationTitleNew Journal of Chemistry
oaire.citationVolume47
oaire.fundingReferenceANID POSTDOCTORAL 3210271, 3230141
oaire.fundingReferenceANID FONDECYT 1220442, 1201880
oaire.fundingReferenceANID FONDAP 15110019
oaire.fundingReferenceANID MILLENNIUM NCN2021_090
oaire.fundingReferenceANID ACT 210057
oaire.licenseConditionCopyright © Royal Society of Chemistry, 2023
oaire.resourceTypeArtículo
oaire.resourceType.enArticle
relation.isAuthorOfPublication7073b065-ad61-4799-9cbf-45500a019334
relation.isAuthorOfPublication.latestForDiscovery7073b065-ad61-4799-9cbf-45500a019334
uct.catalogadorjvu
uct.comunidadRecursos Naturalesen_US
uct.departamentoDepartamento de Ciencias Biológicas y Químicas
uct.facultadFacultad de Recursos Naturales
uct.indizacionScience Citation Index Expanded - SCIE
uct.indizacionScopus
uct.indizacionChemical Abstracts Service (CAS)
Files
Collections
Producción Alimentaria