Mechanistical Insights into the Ultrasensitive Detection of Radioactive and Chemotoxic UO22+ Ions by a Porous Anionic Co-Metal-Organic Framework.

Development of a simple, cost-efficient, and portable UO22+ sensory probe with high selectivity and sensitivity is highly desirable in the context of monitoring radioactive contaminants. Herein, we report a luminescent Co-based metal-organic framework (MOF), {[Me2NH2]0.5[Co(DATRz)0.5(NH2BDC)]·xG}n (1), equipped with abundant amino functionalities for the selective detection of uranyl cations. The ionic structure consists of two types of channels decorated with plentiful Lewis basic amino moieties, which trigger a stronger acid-base interaction with the diffused cationic units and thus can selectively quench the fluorescence intensity in the presence of other interfering ions. Furthermore, the limit of detection for selective UO22+ sensing was achieved to be as low as 0.13 µM (30.94 ppb) with rapid responsiveness and multiple recyclabilities, demonstrating its excellent efficacy. Density functional theory (DFT) calculations further unraveled the preferred binding sites of the UO22+ ions in the tubular channel of the MOF structure. Orbital hybridization between NH2BDC/DATRz and UO22+ together with its significantly large electron-accepting ability is identified as responsible for the luminescence quenching. More importantly, the prepared 1@PVDF {poly(vinylidene difluoride)} mixed-matrix membrane (MMM) displayed good fluorescence activity comparable to 1, which is of great significance for their practical employment as MOF-based luminosensors in real-world sensing application.

Nature and energetics of low-lying excited singlets/triplets and intersystem crossing rates in selone analogs of perylenediimide: A theoretical perspective.

The structural rigidity and chemical diversity of the highly fluorescent perylenediimide (PDI) provide wide opportunities for developing triplet photosensitizers with sufficiently increased energy efficiency. Remarkably high intersystem crossing (ISC) rates with a complete fluorescence turn-off reported recently for several thione analogs of PDI due to substantially large spin-orbit coupling garners huge attention to develop other potential analogs. Here, several selone analogs of PDI, denoted as mSe-PDIs (m = 1-4) with varied Se content and positions, are investigated to provide a comprehensive and comparative picture down the group-16 using density functional theory (DFT) and time-dependent DFT implementing optimally tuned range-separated hybrid in toluene dielectric. All mSe-PDIs are confirmed to be dynamically stable and also thermodynamically feasible to synthesize from their oxygen and thione congeners. The first excited-state singlet (S1) of mSe-PDI with relatively low Se-content (m = 1, 2) is of nπ* character with an expected fluorescence turn-off. Whereas, the ππ* nature of the S1 for 3Se-PDI and 4Se-PDI suggests a possible fluorescence turn-on in the absence of any other active nonradiative deactivation pathways. However, ∼4-6 orders greater ISC rates (∼1012-1014 s-1) than the fluorescence ones (∼108 s-1) for all mSe-PDIs signify highly efficient triplet harvest. Importantly, significantly higher ISC rates for these mSe-PDIs than their thione congeners render them efficient triplet photosensitizers.

Does the Intersystem Crossing Rate of ß-Iodinated Phosphorus Corrole Depend on Iodine Numbers and/or Positions?

The heavy-atom effect is known to enhance the intersystem crossing (ISC) in organic molecular systems. Effects of iodine numbers and positions on the ISC rate of a few meso-difluorophenyl substituted ß-iodinated phosphorus corroles (PCs) with axially ligated fluorine atoms (mI-FPC; m = 1-4) are studied using a time-dependent optimally tuned range-separated hybrid. Solvent effects are accounted for through a polarizable continuum model with a toluene dielectric. Calculations suggest similar thermodynamic stability for all mI-FPCs and also reproduce the experimentally measured 0-0 energies for some of the freebase phosphorus corrole (FPC) systems studied here. Importantly, our results reveal that all mI-FPCs display 10 times larger ISC rate (∼109 s-1) than the fluorescence rate (∼108 s-1), and the higher ISC rate stems from the improved spin-orbit coupling (SOC) introduced by lighter heteroatoms like central P and biaxial F rather than the I heavy-atom effect. However, an enhanced SOC is found with increasing I content for El-Sayed forbidden ISC channels. Research findings reported in this study unveil the impact of light heteroatoms and heavy atoms in promoting ISC in several iodinated PCs, which help in designing visible-light-driven efficient triplet photosensitizers.

Assessing Intersystem Crossing Rates in Donor- and/Acceptor-Functionalized Corroles: A Computational Study.

Small singlet-triplet gap (ΔES-T) and large spin-orbit coupling (SOC) between the low-lying excited spin singlet and triplet states greatly promote the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes that are keys to harvest the triplet population. The electronic structure of a molecule, which strongly depends on its geometry, governs the ISC/RISC. Herein, we have studied visible-light-absorbing freebase corrole and its electron donor/acceptor functional derivatives to explore and understand the effect of homo/hetero meso-substitution in the modulation of corrole photophysical characteristics using time-dependent density functional theory implementing optimally tuned range-separated hybrid. Dimethylaniline and pentafluorophenyl are considered as the representative donor and acceptor functional groups, respectively. Solvent effects are accounted for using a polarizable continuum model with the dichloromethane dielectric. Calculations reproduce the experimentally measured 0-0 energies for some of the functional corroles studied here. Importantly, results reveal that both the homo- and hetero-substituted corroles including the unsubstituted one show substantial ISC rates (∼108 s-1) that are comparable to the fluorescence rates (∼108 s-1). On the other hand, while homo-substituted corroles exhibit modest RISC rates (∼104 - 106 s-1), hetero-substituted ones show relatively lower RISC rates (∼103 - 104 s-1). These results together suggest that both homo- and hetero-substituted corroles could act as triplet photosensitizers, which is also evident from some experimental reports on modest singlet oxygen quantum yield. Calculated rates are analyzed with respect to the variation of ΔES - T and SOC, and their dependence on the molecular electronic structure was evaluated in detail. The research findings reported in this study will add to understanding rich photophysical properties of functional corroles and also aid in devising molecular-level design strategies for developing heavy-atom free functional corroles or related macrocycles for applications in lighting, photocatalysis, photodynamic therapy, etc.