Reconsideration of the Detection and Fluorescence Mechanism of a Pyrene-Based Chemosensor for TNT

Lu, Ming; Zhou, Panwang; Ma, Yinhua; Tang, Zhe; Yang, Yanqiang; Han, Keli

doi:10.1021/acs.jpca.7b11739

Cited by 35 publications

(17 citation statements)

References 48 publications

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“…Although time‐dependent density functional theory (TDDFT) has become the most wide‐spread ab initio model to explore the electronically excited state properties of medium and large molecules due to its balance between computational efficiency and accuracy of results, using this model to deal with biradicals and conical intersections where double excitations play significant roles is difficult . TDDFT with certain conventional approximate functional typically underestimates the excitation energies of charge transfer (CT) states, and range‐separated (RS) functionals can be used as alternatives .…”

Section: Introductionmentioning

confidence: 99%

Why the lowest electronic excitations of rhodamines are overestimated by time‐dependent density functional theory

Zhou

2018

Int J of Quantum Chemistry

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Rhodamines are widely used as laser dyes and fluorescent probes due to their excellent photophysical and photochemical properties. Previous theoretical studies have shown that the lowest excitation energies of rhodamines are overestimated systematically by time‐dependent density functional theory (TDDFT). In this study, we first perform a TDDFT benchmark study with 21 exchange‐correlation functionals (XCFs) on a series of rhodamines and assess the performance of different types of functional in predicting the lowest excitation energies of rhodamines. Statistical results reveal that the fraction of Hartree–Fock exchange (HFX) included in the XCF is a key parameter. Pure functionals without HFX offer the best performance, with the mean absolute error (MAE) of approximately 0.1 eV. However, they provide a wrong order of the lowest nπ* and ππ* states and suffer from charge‐transfer contamination problem for rhodamine dyes (RDs) in zwitterionic form. Among the other tested functionals, popular global hybrid functional B3LYP delivers the smallest MAE of 0.36 eV. We then perform calculations with second‐order algebraic diagrammatic construction and extended multiconfiguration quasi‐degenerate perturbation theory at second‐order of PT expansion methods. Remarkably accurate results are obtained. We confirm that the reason for the overestimation of the lowest excitation energies of RDs by TDDFT method should be similar to that of cyanine dyes, and that double excitations contribute to this systematic deviation.

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Section: Introductionmentioning

confidence: 99%

Why the lowest electronic excitations of rhodamines are overestimated by time‐dependent density functional theory

Zhou

2018

Int J of Quantum Chemistry

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“…Both compounds showed sensitive fluorescence quenching in response to TNT at concentrations of 10 -5 to 10 -4 M. The quenching effect can be explained by photoinduced electron transfer (PET) from relatively electronrich tetraaryl-AQs to electron-deficient TNT molecules. [38] Interestingly, the fluorescence quenching of 1b by TNT gives a linear correlation with TNT concentration, while for compound 1a the correlation fits well into a nonlinear exponential function. The Stern-Volmer plot of 1b quenched with TNT exhibits a curved shape that indicates the occurrence of both static and dynamic quenching ( Figure S-19, Supporting Information).…”

Section: Fluorescence Sensing For Tnt With Tetraaryl-aqsmentioning

confidence: 95%

Highly Twisted Aryl‐Anthraquinodimethanes: Synthesis, Characterization, and Fluorescence Sensing of TNT

Zreid

Tabasi

et al. 2020

Eur J Org Chem

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A series of anthraquinodimethane (AQ) derivatives substituted with sterically hindered arene groups, including pyrene, tetraphenylethene (TPE), and anthracene, was successfully synthesized through Suzuki–Miyaura cross‐coupling reactions under optimized conditions. The molecular structures of these aryl‐substituted AQs were determined by single‐crystal X‐ray diffraction (XRD) analysis, while their electrochemical and electronic properties were investigated by cyclic voltammetric (CV), UV/Vis absorption, and fluorescence spectroscopic analyses. Our studies provide an in‐depth understanding of the structure‐property relationships for sterically hindered aryl‐AQ systems. Interesting aggregation‐induced emission (AIE) properties for tetrapyrenyl‐ and tetra(TPE)‐substituted AQs were further disclosed, based on which the applicability of these compounds as highly sensitive fluorescent probes for nitroaromatic explosives such as 2,4,6‐trinitrotoluene (TNT) was demonstrated.

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“…49 Based on the sign of the second eigenvalue of the electron-density Hessian matrix (λ 2 ), it is possible to discriminate both stabilizing and destabilizing interactions. [34,68] The NCI analysis is performed for Zn-MOF-NB and Zn-MOF-toluene systems. We identified peaks in the region of negative values of the λ 2 , between 0.05 and 0.01 a.u., that indicate the hydrogen bonding interactions of Zn-MOF with NB; see Figure S6.…”

Section: Host-guest Interaction Analysis Via Nci Indexmentioning

confidence: 99%

Sensing mechanism elucidation of a chemosensor based on a metal‐organic framework selective to explosive aromatic compounds

Hidalgo‐Rosa

Treto‐Suárez

Schott

et al. 2020

Int J of Quantum Chemistry

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Theoretical elucidation of the turn-off mechanism of the luminescence of a chemosensor based on a metal-organic framework (MOF) [Zn 2 (OBA) 4 (BYP) 2 ] (BYP: 4,4 0bipyridine; H 2 OBA: 4,4 0-oxybis[benzoic acid]), selective to nitrobenzene (NB) via quantum chemical computations, is presented. The electronic structure and optical properties of Zn-MOF were investigated through the combination of density functional theory (DFT) and time-dependent DFT methods. Our results indicate that the fluorescence emission is governed by a linker (BPY)-to-linker (OBA) charge transfer (LLCT) involving orbitals π-type. Next, the interaction with the analyte was analyzed, where very interesting results were obtained, that is, the lowest unoccupied molecular orbital is now composed of orbitals from NB, which changes the emissive state of the Zn-MOF. This suggests that the LLCT process is blocked, inducing the fluorescence quenching. Otherwise, the Morokuma-Ziegler energy decomposition and natural orbitals for chemical valence on the Zn-MOF-NB interactions were studied in detail, which illustrate the possible channels of charge transfer between Zn-MOF and NB. Finally, we believe that this proposed methodology can be applied to different chemosensor-analyte systems to evidence the molecular and electronic factors that govern the sensing mechanisms.

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Reconsideration of the Detection and Fluorescence Mechanism of a Pyrene-Based Chemosensor for TNT

Cited by 35 publications

References 48 publications

Why the lowest electronic excitations of rhodamines are overestimated by time‐dependent density functional theory

Why the lowest electronic excitations of rhodamines are overestimated by time‐dependent density functional theory

Highly Twisted Aryl‐Anthraquinodimethanes: Synthesis, Characterization, and Fluorescence Sensing of TNT

Sensing mechanism elucidation of a chemosensor based on a metal‐organic framework selective to explosive aromatic compounds

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