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Detection and Characterization of Halogen Bonds by UV-Vis Spectrophotometry and Molecular Modelling
Detección y caracterización de enlaces halógenos por medio de espectrofotometría UV-Vis y modelado molecular
Detecção e caracterização de ligações halógenas através de espectrofotometria UV-Vis e modelagem molecular
DOI:
https://doi.org/10.15446/rev.colomb.quim.v53n2.116648Palabras clave:
Halogen bonds, UV-Vis spectrophotometry, molecular modelling, electronic transitions (en)ligações de halogéneo, espectrofotometria UV-Vis, modelagem molecular, transições eletrônicas (pt)
enlaces de halógeno, espectrofotometría UV-Vis, modelado molecular, transiciones electrónicas (es)
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This study investigates halogen bonds (XBs) in bromine-acetone complexes (Br₂···Ac) using UV-Vis spectrophotometry and computational methods. Electronic structure calculations, including geometry optimizations and excited-state calculations, were carried out using the Gaussian 16 program. Time-Dependent Density Functional Theory (TD-DFT) method, with the M06-2X functional and def2-TZVP basis set, was employed to determine absorption energies corresponding to HOMO→LUMO transitions. Acetone solvation was simulated using the Polarizable Continuum Model (PCM). Experimental UV-Vis spectra of gaseous Br₂ revealed two absorption peaks at 238 nm (λ1,exp) and 454 nm (λ2,exp). Upon dissolution in acetone, λ2,exp underwent a hypsochromic (blue) shift, reaching 395 nm and 365 nm at 0.04 and 0.01 M Br2, respectively. This shift is attributed to XB formation, supported by theoretical spectra showing peaks at 390 nm (Br2···Ac) and 360 nm (Ac···Br2···Ac). The 238 nm peak in Br2(g) is associated with Br2···Br2 complexes, corroborated by a theoretical peak at 240 nm. A single peak at 415 nm in Br2(g) diluted in air is attributed to Br2···N2 complexes, with a corresponding theoretical peak at 417 nm. Theoretical and experimental data align well, validating the methodology and highlighting the role of XBs and electronic transitions in modulating Br2 spectrophotometric properties.
Este estudio analiza los enlaces de halógeno (XBs) en complejos de bromo y acetona (Br2···Ac) mediante espectrofotometría UV-Vis y métodos computacionales. Se realizaron cálculos de estructura electrónica, optimización geométrica y estados excitados con el programa Gaussian 16. Se empleó el método de la teoría del funcional de la densidad dependiente del tiempo (TD-DFT), con el funcional M06-2X y la base def2-TZVP, para calcular energías de absorción correspondientes a transiciones HOMO→LUMO. La solvatación en acetona se simuló usando el Modelo de Continuo Polarizable (PCM). Los espectros UV-Vis experimentales de Br2 gaseoso mostraron picos de absorción a 238 nm (λ1,exp) y 454 nm (λ2,exp). Al disolverse en acetona, λ2,exp presentó un corrimiento hipsoacrómico que se observó a 395 y 365 nm para concentraciones de 0,04 y 0,01 M, respectivamente. Este cambio se atribuye a la formación de XBs, respaldado por espectros teóricos con picos a 390 nm (Br2···Ac) y 360 nm (Ac···Br2···Ac). El pico a 238 nm se asocia con complejos Br2···Br2, confirmado teóricamente a 240 nm. Un único pico a 415 nm en Br2 diluido en aire se atribuye a complejos Br2···N2, con pico teórico a 417 nm. La concordancia entre datos teóricos y experimentales valida la metodología y destaca el papel de los XBs en las propiedades espectrofotométricas del Br2.
Este estudo investiga as ligações de halogênio (XBs) em complexos de bromo e acetona (Br2···Ac) por meio de espectrofotometria UV-Vis e métodos computacionais. Realizaram-se cálculos de estrutura eletrônica, otimizações geométricas e estados excitados com o programa Gaussian 16. O método da teoria funcional da densidade dependente do tempo (TD-DFT) foi empregado, com o funcional M06-2X e o conjunto de base def2-TZVP, para calcular as energias de absorção correspondentes às transições HOMO→LUMO. A solvação em acetona foi simulada com o Modelo de Continuum Polarizável (PCM). Os espectros UV-Vis experimentais de Br2 gasoso revelaram picos de absorção em 238 nm (λ1,exp) e 454 nm (λ2,exp). Ao ser dissolvido em acetona, λ2,exp apresentou um deslocamento hipsoacrômico, observando-se em 395 e 365 nm para concentrações de 0,04 e 0,01 M, respectivamente. Esse deslocamento é atribuído à formação de XBs, sustentada por espectros teóricos com picos em 390 nm (Br2···Ac) e 360 nm (Ac···Br2···Ac). O pico em 238 nm está relacionado a complexos Br2···Br2, confirmado por cálculo teórico em 240 nm. Um único pico em 415 nm para Br2 diluído em ar é atribuído a complexos Br2···N2, com pico teórico em 417 nm. Os dados teóricos e experimentais mostram boa concordância, validando a metodologia e destacando o papel dos XBs nas propriedades espectrofotométricas do Br2.
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