Assembling Near-Infrared Dye on the Surface of Near-Infrared Silica-Coated Copper Sulphide Plasmonic Nanoparticles.

Functionalization of colloidal nanoparticles with organic dyes, which absorb photons in complementary spectral ranges, brings a synergistic effect for harvesting additional light energy. Here, we show functionalization of near-infrared (NIR) plasmonic nanoparticles (NPs) of bare and amino-group functionalized mesoporous silica-coated copper sulphide (Cu2-xS@MSS and Cu2-xS@MSS-NH2) with specific tricarbocyanine NIR dye possessing sulfonate end groups. The role of specific surface chemistry in dye assembling on the surface of NPs is demonstrated, depending on the organic polar liquids or water used as a dispersant solvent. It is shown that dye binding to the NP surfaces occurs with different efficiency, but mostly in the monomer form in polar organic solvents. Conversely, the aqueous medium leads to different scenarios according to the NP surface chemistry. Predominant formation of the disordered dye monomers occurs on the bare surface of mesoporous silica shell (MSS), whereas the amino-group functionalized MSS accepts dye predominantly in the form of dimers. It is found that the dye-NP interaction overcomes the dye-dye interaction, leading to disruption of dye J-aggregates in the presence of the NPs. The different organization of the dye molecules on the surface of silica-coated copper sulphide NPs provides tuning of their specific functional properties, such as hot-band absorption and photoluminescence.

Impact of the thermal properties of the environment on the hot-band absorption-assisted single-photon upconversion.

Single-photon hot-band absorption-assisted anti-Stokes photoluminescence (ASPL) is a non-equilibrium process which causes a local cooling effect and which therefore is accompanied by a reverse heat flux from the warmer environment. Here, we demonstrate that the thermal properties of the medium, i.e., its thermal conductivity and specific heat capacity, play a significant role in driving the ASPL of an emitter placed in it. Exploiting seven different solvents and the near-infrared tricarbocyanine dye as a single-photon upconverter, we show an obvious correlation of activation energy and the quantum yield (QY) of ASPL with the solvent thermal conductivity and specific heat capacity, respectively. A linear fit of the above correlations leads to the predictions that the maximum QY of ASPL should be observed in a vacuum where it should reach a value of ∼10% for the exploited dye, which is close to the QY of its Stokes emission and that the high thermal conductivity of the solvent assists in a stepwise population of the hot band, which thus facilitates the hot-band absorption-assisted ASPL. These findings lead to the conclusion that the selection of a solvent with appropriate thermal properties may help one to control the efficiency of the one-photon energy upconversion.

"Awakening" of the S2 Emission of Tricarbocyanine Dyes Stimulated by Interaction with Carbon Quantum Dots.

Anti-Kasha emission (i.e., the emission from Sn (n > 1) excited levels) of infrared chromophores which possess intensive absorption and S1 emission in the near-infrared region, but which are spectrally silent in the visible, is a challenging task for relevant applications such as energy conversion, bioimaging, sensitization of solar cells, optical sensors, and so on. Here we demonstrate a dual emission of near-infrared tricarbocyanine dyes with a bright green S2 fluorescence, whose quantum yield increases by 2-4 times together with a strong enhancement of the spontaneous rate of S2 fluorescence, whereas the quantum yield of S1 emission decreases by 2-7 times, respectively, as a result of immobilization of the dye molecule via interaction with carbon quantum dots. The enhanced immobilization-induced S2 emission is shown to occur because of planarization of the molecule and freezing its rotational degrees of freedom as indicated by suppression of the dye hot-band absorption-assisted anti-Stokes S1 emission.

Reversible Charge Transfer with Single-Walled Carbon Nanotubes Upon Harvesting the Low Energy Part of the Solar Spectrum.

Here, the ability of a novel near-infrared dye to noncovalently self-assemble onto the surface of single-walled carbon nanotubes (SWCNTs) driven by charge-transfer interactions is demonstrated. Steady-state, Raman, and transient absorption spectroscopies corroborate the electron donating character of the near-infrared dye when combined with SWCNTs, in the form of fluorescence quenching of the excited state of the dye, n-doping of SWCNTs, and reversible charge transfer, respectively. Formation of the one-electron oxidized dye as a result of interactions with SWCNTs is supported by spectroelectrochemical measurements. The ultrafast electronic process in the near-infrared dye, once immobilized onto SWCNTs, starts with the formation of excited states, which decay to the ground state via the intermediate population of a fully charge-separated state, with characteristic time constants for the charge separation of 1.5 ps and charge recombination of 25 ps, as derived from the multiwavelength global analysis. Of great relevance is the fact that charge-transfer occurs from the hot excited state of the near-infrared dye to SWCNTs.

Sensitization of upconverting nanoparticles with a NIR-emissive cyanine dye using a micellar encapsulation approach.

Photon upconversion nanomaterials have a wide range of applications, including biosensing and deep-tissue imaging. Their typically very weak and narrow absorption bands together with their size dependent luminescence efficiency can limit their application potential. This has been addressed by increasingly sophisticated core-shell particle architectures including the sensitization with organic dyes that strongly absorb in the near infrared (NIR). In this work, we present a simple water-dispersible micellar system that features energy transfer from the novel NIR excitable dye, 1859 SL with a high molar absorption coefficient and a moderate fluorescence quantum yield to oleate-capped NaYF4:20%Yb(III), 2%Er(III) upconversion nanoparticles (UCNP) upon 808 nm excitation. The micelles were formed using the surfactants Pluronic F-127 and Tween 80 to produce a hydrophilic dye-UCNP system. Successful energy transfer from the dye to the UCNP could be confirmed by emission measurements that revealed the occurrence of upconversion emission upon excitation at 808 nm and an enhancement of the green Er(III) emission compared to direct Er(III) excitation at 808 nm.

Excimer Emission in J-Aggregates.

An excimer in J-aggregates has been often considered as a self-trapped exciton originating from the free exciton excited on the same aggregate and relaxed through interaction with vibronic modes. Here we show that other types of excimers due to intermolecular off-diagonal interactions can be observed in J-aggregates of thiamonomethinecyanine dyes. These excimers arise owing to free excitons too, but they possess a longer formation time of more than 100 ps, indicating migration of free excitons to the excimer formation site, where they interact with a guest species in the ground state. Formation of the excimers occurs in solutions as a power law of concentration with an exponent of 1.5, showing that an excited aggregate should be twice longer than a ground-state guest species, consistent with the exciton coherence length of four molecules versus one dimer, respectively. Unlike the self-trapped exciton, lower temperatures lead to significant suppression of the observed excimer emission.

Fluorescent J-aggregates of cyanine dyes: basic research and applications review.

J-aggregates are fascinating fluorescent nanomaterials formed by highly ordered assembly of organic dyes with the spectroscopic properties dramatically different from that of single or disorderly assembled dye molecules. They demonstrate very narrow red-shifted absorption and emission bands, strongly increased absorbance together with the decrease of radiative lifetime, highly polarized emission and other valuable features. The mechanisms of their electronic transitions are understood by formation of delocalized excitons already on the level of several coupled monomers. Cyanine dyes are unique in forming J-aggregates over the broad spectral range, from blue to near-IR. With the aim to inspire further developments, this review is focused on the optical characteristics of J-aggregates in connection with the dye structures and on their diverse already realized and emerging applications.