Tailoring intersystem crossing in phosphorus corroles through axial chalcogenation: a detailed theoretical study.

Intersystem crossing (ISC) of visible-light absorbing metal-free corrole macrocycles can be greatly tuned by means of suitable chemical functionalization. Axially chalcogenated phosphorus corrole derivatives (XPCs; X = O, S, Se) are expected to show large spin-orbit coupling (SOC) the heavy-atom effect and therefore a much improved ISC. Excited-state deactivation of XPCs including PC is studied using time-dependent optimally tuned range-separated hybrid functionals combined with a polarizable continuum model with toluene as a dielectric medium to account for polar solvent effects.

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

Development of a simple, cost-efficient, and portable UO 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), {[MeNH][Co(DATRz)(NHBDC)]·G} (), 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.

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.

Does the Intersystem Crossing Rate of β-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 β-iodinated phosphorus corroles (PCs) with axially ligated fluorine atoms (I-FPC; = 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.

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

Small singlet-triplet gap (Δ) 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.