Nonaromatic Organonickel(II) Phototheranostics.

Earth-abundant metal-based theranostics, agents that integrate diagnostic and therapeutic functions within the same molecule, may hold the key to the development of low-cost personalized medicines. Here, we report a set of O-linked nonaromatic benzitripyrrin (C^N^N^N) macrocyclic organonickel(II) complexes, -, containing strong σ-donating M-C bonds. Complexes - are characterized by a square-planar coordination geometry as inferred from the structural studies of .

Unusual near infrared (NIR) fluorescent palladium(ii) macrocyclic complexes containing M-C bonds with bioimaging capability.

Near infrared (NIR) luminescent metal complexes are promising probes in bioimaging and biosensing, however they generally suffer from oxygen interference arising from heavy metal effects. We designed new tetradentate macrocyclic benzitripyrrin (C^N^N^N) ligands by combination of M-C bond formation and reducing the π-conjugation to achieve NIR fluorescent Pd complexes (700-1000 nm) with quantum yields up to 14%. To understand the origin of NIR fluorescence, detailed analyses by density functional theory/time-dependent density functional theory (DFT/TDDFT) calculations together with femtosecond and nanosecond transient absorption spectroscopies suggest that M-C bond formation indeed leads to destabilization of the d-d excited state and less effective quenching of emission; and importantly, small spin-orbital coupling (SOC) and the large singlet-triplet energy gap are the primary causes of the non-population of triplet states.

An ART-based construction of RBF networks.

Radial basis function (RBF) networks are widely used for modeling a function from given input-output patterns. However, two difficulties are involved with traditional RBF (TRBF) networks: The initial configuration of an RBF network needs to be determined by a trial-and-error method, and the performance suffers when the desired output has abrupt changes or constant values in certain intervals. We propose a novel approach to over.