Harnessing the benzyne insertion consequence to enable π-extended pyrido-acridine and quinazolino-phenanthridine.

Distinct protocols have been devised for the preparation of hybrid heterocyclic scaffolds like π-extended pyrido-acridines and quinazolino-phenanthridines duly materialized through Rh(III)- and Pd(II)-mediated catalytic courses commencing from acridine and quinazolimine scaffolds. Interestingly, the parent compounds (acridines and quinazolimines) are actualized from 2-aminobenzonitrile and anthranilic acid, where 2-aminobenzonitrile acts as the 1,4-dipolarophilic species and anthranilic acid as the benzyne precursor. The molecular assembly of acridine suggests the participation of two benzyne units. In addition, the structural motif of the quinazolimine ring features one benzyne unit. Further, indolizine ring containing the enaminonitrile skeleton upon exposure to benzyne forms an indolizine fused quinoline ring, decorated with three benzyne units.

Ultrafast dynamics and ultrasensitive single particle spectroscopy of optically robust core/alloy shell semiconductor quantum dots.

A "one-pot one-step" synthesis method of Core/Alloy Shell (CAS) quantum dots (QDs) offers the scope of large scale synthesis in a less time consuming, more economical, highly reproducible and high-throughput manner in comparison to "multi-pot multi-step" synthesis for Core/Shell (CS) QDs. Rapid initial nucleation, and smooth & uniform shell growth lead to the formation of a compositionally-gradient alloyed hetero-structure with very significantly reduced interfacial trap density in CAS QDs. Thus, interfacial strain gets reduced in a much smoother manner leading to enhanced confinement for the photo-generated charge carriers in CAS QDs. Convincing proof of alloy-shelling for a CAS QD has been provided from HRTEM images at the single particle level. The band gap could be tuned as a function of composition, temperature, reactivity difference of precursors, etc. and a high PLQY and improved photochemical stability could be achieved for a small sized CAS QD. From the ultrafast exciton dynamics in CdSe and InP CAS QDs, it has been shown that (a) the hot exciton thermalization/relaxation happens in <500 fs, (b) hot electron trapping dynamics occurs within a ∼1 ps time scale, (c) band edge exciton trapping occurs within a 10-25 ps timescale and (d) for CdSe CAS QDs the hot hole gets trapped in about 35 ps. From fast PL decay dynamics, it has been shown that the amplitude of the intermediate time constant can be correlated with the PLQY. A model has been provided to understand these ultrafast to fast exciton dynamical processes. At the ultrasensitive single particle level, unlike CS QDs, CdSe CAS QDs have been shown to exhibit (a) constancy of PLmax (i.e. no bluing) and (b) constancy of PL intensity (i.e. no bleaching) of the single CAS QDs for continuous irradiation for one hour under an air atmosphere. Thus, CAS QDs hold the promise of being a superior optical probe in comparison to CS QDs both at the ensemble and at the single particle level, leading to enhanced flexibility of the CAS QDs towards designing and developing next generation application devices.

meta-Fluorophores: an uncharted ocean of opportunities.

meta-Fluorophores (MFs) are unique ultra-light (in terms of molecular weight (MW)) fluorophores exhibiting luminescence with a wide colour gamut ranging from blue to the NIR. Single benzenic MFs are easy to synthesize, are quite bright (with photoluminescence quantum yield (PLQY) as high as 63%) and exhibit very large Stokes shift (as high as 260 nm (8965 cm-1)), with large solvatochromic shift (as high as 175 nm), and very long excited-state-lifetime (as high as 26 ns) for such ultra-light fluorophores. An emission maximum of ≥600 nm has been achieved with an MF in a polar medium having a MW of only 177 g mol-1 and in a nonpolar medium having MW of only 255 g mol-1; therefore, a large-sized π-conjugated para-fluorophore is no longer a prerequisite for red/NIR emission. Structurally varied MFs pave the way for creating an ocean of opportunities and are thus promising for replacing para-fluorophores for different applications, ranging from bioimaging to LEDs.

Beneficial Intrinsic Hole Trapping and Its Amplitude Variation in a Highly Photoluminescent Toxic-Metal-Free Quantum Dot.

Intrinsic hole trapping as well as hole detrapping have not been observed for any quantum dot (QD) or perovskite nanocrystal (PNC) system. Moreover, amplitude variation of intrinsic hole trapping (or detrapping) has not been reported at all for any QD or PNC system. However, for a CuInS2-based core/alloy-shell (CAS) QD system, (a) both intrinsic hole trapping and detrapping have been observed and (b) very significant amplitude variations of hole trapping (∼16 to ∼42%) and hole detrapping (∼44 to 23%) have been observed. Unlike detrimental electron trapping, hole trapping has been shown to be beneficial, having a direct correlation toward increasing PLQY to 96%. Simultaneous electron and hole trapping has been shown to be quite beneficial for the CuInS2-based CAS QD system leading to the longest ON time (∼130 s) for which a nontoxic metal-based QD remains only in the ON-state without blinking.

Transforming exciton dynamics in perovskite nanocrystal through Mn doping.

Zn-alloyed CsPb(Cl/Br)3 perovskite nanocrystals (PNCs) have been synthesized and used as a model system for Mn doping in order to understand the effect of Mn doping on exciton dynamics. While keeping the PL emission maximum and PLQY of both PNC samples nearly the same, the radiative decay rate of the host band decreases ∼6.5 times and the non-radiative decay rate increases ∼2.5 times upon Mn doping. Unlike reports in the literature in which the dopant emission decreases to near-zero, in the present case we observe ∼5.5-fold enhancement of the integrated PL intensity of the dopant emission when the temperature decreases from 290 K to 190 K. Interestingly, the FWHM of the host PL emission band increases with a decrease in temperature from 290 K to 190 K. A higher value of phonon energy in PNC2 (58 ± 2 meV) in comparison to CsPbBr3 has been noted. The low magnitude of the Huang-Rhys factor indicates less electron phonon coupling for the Mn-doped PNC system. Temperature-dependent dopant PL decay exhibits biexponential decay behaviour with time constants τ1 = 450-540 µs and τ2 = 1.1-1.2 ms. With a decrease in temperature from 290 K to 190 K, the amplitude of the faster component decreases from 80% to 60%; concomitantly, the amplitude of the slower component increases from 20% to 40%. Ultrasensitive single-particle spectroscopic analyses reveal that, although the probability density distributions (PDDs) of the durations of both ON and OFF events of PNC1 could be fitted with a truncated inverse power law (TIPL), however, for PNC2, both PDDs could be fitted with an inverse power law (IPL). A comparatively lower value of the power law exponent mON indicates a higher probability of longer ON events for PNC1 than for PNC2. Truncation in the PDDs of both ON and OFF events has been observed for PNC1, but not in the PDDs of either ON or OFF events for PNC2. The presence of shallow trap states is responsible for the truncation for PNC1, whereas the presence of deep dopant states does not allow truncation in the host PL emission of PNC2. All these observations clearly demonstrate that Mn doping transforms the host PL exciton dynamics for Zn-alloyed Mn-doped CsPb(Cl/Br)3 PNCs very significantly.

Excitation-Energy-Dependent Photoluminescence Quantum Yield is Inherent to Optically Robust Core/Alloy-Shell Quantum Dots in a Vast Energy Landscape.

The importance of alloy-shelling in optically robust Core/Alloy-Shell (CAS) QDs has been described from structural and energetic aspects. Unlike fluorescent dyes, both Core/Shell (CS) and CAS QDs exhibit excitation-energy-dependent photoluminescence quantum yield (PLQY). For both CdSe and InP CAS QDs (with metal- and nonmetal-based alloy-shelling, respectively), with increasing excitation energy, (a) the ultrafast rise-time or relaxation-time to the band-edge increases and (b) the magnitude of the normalized bleach signal decreases. Ultrasensitive single-particle spectroscopic investigation results showed that with decreasing excitation energy, (a) the fraction of ON events increases, (b) the ratio of exciton-detrapping rate/trapping rate increases, and (c) the extent of beneficial hole trapping increases. A relative decrease in PLQY with increasing excitation energy is much less pronounced in CAS QDs than in CS QDs. Unless trap states are removed completely especially in the higher-energy landscape, PLQY will remain inherently dependent on excitation energy for QDs in the vast energy landscape. When reporting the PLQY of QDs, the magnitude of the excitation energy must be mentioned.

Near-Ergodic CsPbBr3 Perovskite Nanocrystal with Minimal Statistical Aging.

Optical robustness, uniformity, ergodicity, statistical aging, etc. dictate the applicability of nanocrystals. Based on a series of multimodal statistical analyses such as the Kolmogorov-Smirnov test, Lévy statistics, etc., we demonstrate that for CsPbBr3 perovskite nanocrystals (PNCs): (a) the extent of heterogeneity in the quality and associated physical processes is minimal; (b) the optical robustness is very high, and (c) indeed, a single PNC can depict optical behavior of its ensemble. In addition, toward prospective applications, an optically robust CsPbBr3 PNC exhibits (i) near-ergodicity and (ii) minimal statistical aging, which are extremely vital and complementary to its high defect tolerance.

Unravelling halide-dependent charge carrier dynamics in CsPb(Br/Cl)3 perovskite nanocrystals.

With an increasing bromide content in CsPb(Br/Cl)3 perovskite nanocrystals (PNCs), the steady state photoluminescence quantum yield value increases from 28% to 50% to 76%. Ultrafast transient absorption analyses reveal that the normalized band edge population increases more than two-fold on excitation at the band edge with increasing bromide content, and the hot exciton trapping time increases from 450 fs to 520 fs to 700 fs with increasing bromide content. Ultrasensitive single particle spectroscopic analyses reveal that the peak of the ON fraction distribution increases from 0.65 to 0.75 to 0.85 with increasing bromide content. More specifically, the percentage of PNCs with the ON fraction >75% increases four fold from 24% to 50% to 98% with increasing bromide content. Moreover, the ratio of the detrapping rate and trapping rate increases more than 25 fold with an increase in bromide content, signifying the excitons remaining in the trap state for a smaller time with increasing bromide content. In order to standardize the measurement and analyses, all these three PNCs have the same size and shape, and all the excitations have been made at the same energy above the band edge for all three PNCs and for both ultrafast transient absorption and ultrasensitive single particle measurements.

Near-Unity Photoluminescence Quantum Yield and Highly Suppressed Blinking in a Toxic-Metal-Free Quantum Dot.

There is no literature report of simultaneously achieving near-unity PLQY (ensemble level) and highly suppressed blinking (ultrasensitive single-particle spectroscopy (SPS) level) in a toxic-metal-free QD. In this Letter we report accomplishing near-unity PLQY (96%) and highly suppressed blinking (>80% ON fraction) in a toxic-metal-free CuInS2/ZnSeS Core/Alloy-Shell (CAS) QD. In addition, (i) gigantic enhancement of PLQY (from 15% (Core) to 96% (CAS QD)), (ii) ultrahigh stability over 1 year without significant reduction of PLQY at the ensemble level, (iii) high magnitude (nearly 3 times) of electron detrapping/trapping rate, and (iv) very long ON duration (∼2 min) without blinking at the SPS level enable this ultrasmall (∼3.3 nm) CAS QD to be quite suitable for single-particle tracking/bioimaging. A model explaining all these excellent optical properties has been provided. This ultrabright CAS QD has been successfully utilized toward fabrication of low-cost microcontroller-based stable and bright yellow and white QD-LEDs.

Extent of Shallow/Deep Trap States beyond the Conduction Band Minimum in Defect-Tolerant CsPbBr3 Perovskite Quantum Dot: Control over the Degree of Charge Carrier Recombination.

Perovskite quantum dots (PQDs) are known to be defect-tolerant, possessing a clean band gap with optically inactive benign defect states. However, we show that there exist significant deep trap states beyond the conduction band minimum, although the extent of shallow trap states is observed to be minimal. The extent of deep trap states beyond the conduction band minimum seems to be significant in PQDs; however, the extent is less than that of even optically robust CdSe- and InP-based core/alloy-shell QDs. In-depth analyses based on ultrafast transient absorption and ultrasensitive single-particle spectroscopic investigations decode the underlying degree of charge carrier recombination in CsPbBr3 PQDs, which is quite important for energy applications.

Instantaneous, room-temperature, open-air atmosphere, solution-phase synthesis of perovskite quantum dots through halide exchange employing non-metal based inexpensive HCl/HI: ensemble and single particle spectroscopy.

Herein, the instantaneous synthesis of highly crystalline, uniform-sized (ca. 11.3 ± 0.1 nm), blue-to-green to yellow to red-emitting all-inorganic perovskite quantum dots (CsPbBr3 and mixed halide PQDs) was achieved at room temperature under an open-air atmosphere (no glove box) through halide exchange in the solution phase employing easily available, inexpensive non-metal-based halide sources such as HCl and HI. No complicated pre-treatment of the halide source was required. Moreover, these PQDs were stable for a few weeks under an open-air atmosphere. The PL emission spectra are quite narrow, and the PLQYs are quite high (80% for even Br/I mixed PQDs). At the single particle level, the 〈ON fraction〉 has been noted to vary from 75% to 85% for different PQDs, the m ON values are close to 1.0, and the m OFF values are >1.5. The latter indicates that long ON durations are more probable. The increase in the ON event truncation time (from 2.7 to 4.0 s) and the concomitant decrease in the OFF event truncation time (from 6.6 to 4.3 s) could be correlated with the increase in the PLQY (from 0.55 to 0.75). In addition, an interesting memory effect could be observed in both the ON and the OFF event durations.