Bifurcation of Excited-State Population Leads to Anti-Kasha Luminescence in a Disulfide-Decorated Organometallic Rhenium Photosensitizer.

We report a rhenium diimine photosensitizer equipped with a peripheral disulfide unit on one of the bipyridine ligands, [Re(CO)3(bpy)(S-Sbpy4,4)]+ (1+, bpy = 2,2'-bipyridine, S-Sbpy4,4 = [1,2]dithiino[3,4-c:6,5-c']dipyridine), showing anti-Kasha luminescence. Steady-state and ultrafast time-resolved spectroscopies complemented by nonadiabatic dynamics simulations are used to disclose its excited-state dynamics. The calculations show that after intersystem crossing the complex evolves to two different triplet minima: a (S-Sbpy4,4)-ligand-centered excited state (3LC) lying at lower energy and a metal-to-(bpy)-ligand charge transfer (3MLCT) state at higher energy, with relative yields of 90% and 10%, respectively. The 3LC state involves local excitation of the disulfide group into the antibonding σ* orbital, leading to significant elongation of the S-S bond. Intriguingly, it is the higher-lying 3MLCT state, which is assigned to display luminescence with a lifetime of 270 ns: a signature of anti-Kasha behavior. This assignment is consistent with an energy barrier ≥ 0.6 eV or negligible electronic coupling, preventing reaction toward the 3LC state after the population is trapped in the 3MLCT state. This study represents a striking example on how elusive excited-state dynamics of transition-metal photosensitizers can be deciphered by synergistic experiments and state-of-the-art calculations. Disulfide functionalization lays the foundation of a new design strategy toward harnessing excess energy in a system for possible bimolecular electron or energy transfer reactivity.

Light-harvesting antennae based on copper indium sulfide (CIS) quantum dots.

Copper indium sulfide quantum dots (CIS QDs) and their core-shell analogues (CIS@ZnS QDs) were functionalized with pyrene chromophores via a dihydrolipoamide bifunctional binding moiety: UV excitation of the pyrene chromophores resulted in sensitized emission of the CIS core because of an efficient energy transfer process; the core-shell hybrid system exhibits a 50% increased brightness when excited at 345 nm.

Luminescent copper indium sulfide (CIS) quantum dots for bioimaging applications.

Copper indium sulfide (CIS) quantum dots are ideal for bioimaging applications, by being characterized by high molar absorption coefficients throughout the entire visible spectrum, high photoluminescence quantum yield, high tolerance to the presence of lattice defects, emission tunability from the red to the near-infrared spectral region by changing their dimensions and composition, and long lifetimes (hundreds of nanoseconds) enabling time-gated detection to increase signal-to-noise ratio. The present review collects: (i) the most common procedures used to synthesize stable CIS QDs and the possible strategies to enhance their colloidal stability in aqueous environment, a property needed for bioimaging applications; (ii) their photophysical properties and parameters that affect the energy and brightness of their photoluminescence; (iii) toxicity and bioimaging applications of CIS QDs, including tumor targeting, time-gated detection and multimodal imaging, as well as theranostics. Future perspectives are analyzed in view of advantages and potential limitations of CIS QDs compared to most traditional QDs.

Water-soluble silicon nanocrystals as NIR luminescent probes for time-gated biomedical imaging.

Luminescent probes based on silicon nanocrystals (SiNCs) have many advantages for bioimaging compared to more conventional quantum dots: abundancy of silicon combined with its biocompatibility; tunability of the emission color of SiNCs in the red and NIR spectral region to gain deeper tissue penetration; long emission lifetimes of SiNCs (hundreds of µs) enabling time-gated acquisitions to avoid background noise caused by tissue autofluorescence and scattered excitation light. Here we report a new three-step synthesis, based on a low temperature thiol-ene click reaction that can afford SiNCs, colloidally stable in water, with preserved bright red and NIR photoluminescence (band maxima at 735 and 945 nm for nanocrystals with diameters of 4 and 5 nm, respectively) and long emission lifetimes. Their luminescence is insensitive to dioxygen and sensitive to pH changes in the physiological range, enabling pH sensing. In vivo studies demonstrated tumor accumulation, 48 hours clearance and a 3-fold improvement of the signal-to-noise ratio compared to steady-state imaging.

Amine functionalised silicon nanocrystals with bright red and long-lived emission.

When functionalised with amines, silicon nanocrystals (SiNCs) are known to have surface-state emission with loss of colour tunability, low quantum yield and short nanosecond lifetimes. These changes in optical properties are produced by direct amine bonding on the silicon surface. In this article, secondary amine functionalised SiNCs with bright, red (λmax = 750 nm) and long-lived emission (τ ca. 50 µs) are reported for the first time via a three-step synthetic approach. These SiNCs are colloidally stable in several polar solvents and can be further functionalised by reaction with carboxylic acid groups. We proved the feasibility of further functionalization with pyrene butyric acid: ca. 40 pyrene units per nanoparticle were attached via amide bond formation. The resulting hybrid system works as a light-harvesting antenna: excitation of pyrene units at 345 nm results in sensitised emission at 700 nm by the silicon core.