Dark State Concentration Dependent Emission and Dynamics of CdSe Nanoplatelet Exciton-Polaritons.

The recent surge of interest in polaritons has prompted fundamental questions about the role of dark states in strong light-matter coupling phenomena. Here, we systematically vary the relative number of dark states by controlling the number of stacked CdSe nanoplatelets confined in a Fabry-Pérot cavity. We find the emission spectrum to change significantly with an increasing number of nanoplatelets, with a gradual shift of the dominant emission intensity from the lower polariton branch to a manifold of dark states.

Sub-Diffraction Correlation of Quantum Emitters and Local Strain Fields in Strain-Engineered WSe Monolayers.

Strain-engineering in atomically thin metal dichalcogenides is a useful method for realizing single-photon emitters (SPEs) for quantum technologies. Correlating SPE position with local strain topography is challenging due to localization inaccuracies from the diffraction limit. Currently, SPEs are assumed to be positioned at the highest strained location and are typically identified by randomly screening narrow-linewidth emitters, of which only a few are spectrally pure.

Control of Photoswitching Kinetics with Strong Light-Matter Coupling in a Cavity.

Most photochemistry occurs in the regime of weak light-matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light-matter interactions between an optical field and multiple molecules lead to collective hybrid light-matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules.

Theory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons.

This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of excited state vibrational polaritons (ESVP) via UV/vis excitation only involve vibrational modes with both a non-zero FC activity and IR activity in the excited state.

Chemomechanical modification of quantum emission in monolayer WSe.

Two-dimensional (2D) materials have attracted attention for quantum information science due to their ability to host single-photon emitters (SPEs). Although the properties of atomically thin materials are highly sensitive to surface modification, chemical functionalization remains unexplored in the design and control of 2D material SPEs. Here, we report a chemomechanical approach to modify SPEs in monolayer WSe through the synergistic combination of localized mechanical strain and noncovalent surface functionalization with aryl diazonium chemistry.

Room-Temperature Phosphorescence from Pd(II) and Pt(II) Complexes as Supramolecular Luminophores: The Role of Self-Assembly, Metal-Metal Interactions, Spin-Orbit Coupling, and Ligand-Field Splitting.

The synthesis as well as the structural and photophysical characterization of two isoleptic bis-cyclometalated Pt(II) and Pd(II) complexes, namely [] and [], bearing a tailored dianionic tetradentate ligand () are reported. The isostructural character and intermolecular interactions of [] and [] were assessed by NMR spectroscopy and X-ray diffraction analysis. Both complexes show fully ligand-controlled aggregation, demonstrating that a judicious molecular design can tune the photophysical properties.

Conversion of Classical Light Emission from a Nanoparticle-Strained WSe Monolayer into Quantum Light Emission via Electron Beam Irradiation.

Solid-state single photon emitters (SPEs) within atomically thin transition metal dichalcogenides (TMDs) have recently attracted interest as scalable quantum light sources for quantum photonic technologies. Among TMDs, WSe monolayers (MLs) are promising for the deterministic fabrication and engineering of SPEs using local strain fields. The ability to reliably produce isolatable SPEs in WSe is currently impeded by the presence of numerous spectrally overlapping states that occur at strained locations.

Selective visible-light photocatalysis of acetylene to ethylene using a cobalt molecular catalyst and water as a proton source.

The production of polymers from ethylene requires the ethylene feed to be sufficiently purified of acetylene contaminant. Accomplishing this task by thermally hydrogenating acetylene requires a high temperature, an external feed of H gas and noble-metal catalysts. It is not only expensive and energy-intensive, but also prone to overhydrogenating to ethane.

Back electron transfer rates determine the photoreactivity of donor-acceptor stilbene complexes in a macrocyclic host.

Host-guest 2 : 1 complexation of photoreactive alkene guests improves the selectivity of [2 + 2] photodimerizations by templating alkene orientation prior to irradiation. Host-guest chemistry can also provide 1 : 1 : 1 complexes through the inclusion of electronically complementary donor and acceptor guests, but the photoreactivity of such complexes has not been investigated. We imagined that such complexes could enable selective cross-[2 + 2] photocycloadditions between donor and acceptor stilbenes.

Thick-Layer Lead Iodide Perovskites with Bifunctional Organic Spacers Allylammonium and Iodopropylammonium Exhibiting Trap-State Emission.

The nature of the organic cation in two-dimensional (2D) hybrid lead iodide perovskites tailors the structural and technological features of the resultant material. Herein, we present three new homologous series of (100) lead iodide perovskites with the organic cations allylammonium (AA) containing an unsaturated C═C group and iodopropylammonium (IdPA) containing iodine on the organic chain: (AA)MAPbI ( = 3-4), [(AA)(IdPA)]MAPbI ( = 1-4), and (IdPA)MAPbI ( = 1-4), as well as their perovskite-related substructures. We report the in situ transformation of AA organic layers into IdPA and the incorporation of these cations simultaneously into the 2D perovskite structure.

Dynamic Tuning of the Bandgap of CdSe Quantum Dots through Redox-Active Exciton-Delocalizing N-Heterocyclic Carbene Ligands.

Ligands that enable the delocalization of excitons beyond the physical boundary of the inorganic core of semiconductor quantum dots (QDs), called "exciton-delocalizing ligands (EDLs)", offer the opportunity to design QD-based environmental sensors with dynamically responsive optical spectra, because the degree of exciton delocalization depends on the electronic structure of the EDL. This paper demonstrates dynamic, reversible tuning of the optical bandgap of a dispersion of CdSe QDs through the redox states of their 1,3-dimesitylnaphthoquinimidazolylidene N-heterocyclic carbene (nqNHC) ligands. Upon binding of the nqNHC ligands to the QD, the optical bandgap bathochromically shifts by up to 102 meV.

Investigating Reaction Intermediates during the Seedless Growth of Gold Nanostars Using Electron Tomography.

Good's buffers can act both as nucleating and shape-directing agents during the synthesis of anisotropic gold nanostars (AuNS). Although different Good's buffers can produce AuNS shapes with branches that are oriented along specific crystallographic directions, the mechanism is not fully understood. This paper reports how an analysis of the intermediate structures during AuNS synthesis from HEPES, EPPS, and MOPS Good's buffers can provide insight into the formation of seedless AuNS.

Polariton Dynamics in Two-Dimensional Ruddlesden-Popper Perovskites Strongly Coupled with Plasmonic Lattices.

Strong coupling between light and matter can produce hybrid eigenstates known as exciton-polaritons. Although polariton dynamics are important photophysical properties, the relaxation pathways of polaritons in different coupling regimes have seen limited attention. This paper reports the dynamics of hybridized states from 2D Ruddlesden-Popper perovskites coupled to plasmonic nanoparticle lattices.

Quantum Dots Photocatalyze Intermolecular [2 + 2] Cycloadditions of Aromatic Alkenes Adsorbed to their Surfaces via van der Waals Interactions.

Triplet excited state-initiated photochemistry is a mild and selective route to cycloadditions, radical rearrangements, couplings, fragmentations, and isomerizations. Colloidal quantum dots are proven visible-light photosensitizers and structural scaffolds for triplet-initiated reactions of molecules that are functionalized (with carboxylates) to anchor on the QD surface. Here, with the aid of polyaromatic energy shuttles that act as noncovalent adsorption sites for substrates on the QD surface, the scope of QD-photocatalyzed intermolecular [2 + 2] cycloadditions is extended to freely diffusing substrates (no anchoring groups).

Direct Observation of Modulated Radical Spin States in Metal-Organic Frameworks by Controlled Flexibility.

Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique to a variety of fields. When incorporated in solid state materials, generation of organic radicals proves challenging due to aggregation. Metal-organic frameworks (MOFs) are promising candidates for immobilization and stabilization of organic radicals because of the tunable spatial arrangement of organic linkers and metal nodes, which sequesters the reactive species.

Origin of Low Temperature Trion Emission in CdSe Nanoplatelets.

Colloidal semiconductor nanoplatelets (NPLs) are a scalable materials platform for optoelectronic applications requiring fast and narrow emission, including spin-to-photon transduction within quantum information networks. In particular, three-particle negative trions of NPLs are appealing emitters since, unlike excitons, they do not have an optically "dark" sublevel. In CdSe NPLs, trion emission dominates the photoluminescence (PL) spectrum at low temperature but using them as single photon-emitting states requires more knowledge about their preparation, since trions in these materials are not directly optically accessible from the ground state.

Quantum Dot-Sensitized Photoreduction of CO in Water with Turnover Number > 80,000.

Climate change and global energy demands motivate the search for sustainable transformations of carbon dioxide (CO) to storable liquid fuels. Photocatalysis is a pathway for direct conversion of CO to CO, one step within light-powered reaction networks that could, if efficient enough, transform the solar energy conversion landscape. To date, the best performing photocatalytic CO reduction systems operate in nonaqueous solvents, but technologically viable solar fuels networks will likely operate in water.

Mechanistic Investigation of Molybdenum Disulfide Defect Photoluminescence Quenching by Adsorbed Metallophthalocyanines.

Lattice defects play an important role in determining the optical and electrical properties of monolayer semiconductors such as MoS. Although the structures of various defects in monolayer MoS are well studied, little is known about the nature of the fluorescent defect species and their interaction with molecular adsorbates. In this study, the quenching of the low-temperature defect photoluminescence (PL) in MoS is investigated following the deposition of metallophthalocyanines (MPcs).

Enhanced Exciton Quantum Coherence in Single CsPbBr Perovskite Quantum Dots using Femtosecond Two-Photon Near-Field Scanning Optical Microscopy.

Cesium-halide perovskite quantum dots (QDs) have gained tremendous interest as quantum emitters in quantum information processing applications due to their optical and photophysical properties. However, engineering excitonic states in quantum dots requires a deep knowledge of the coherent dynamics of their excitons at a single-particle level. Here, we use femtosecond time-resolved two-photon near-field scanning optical microscopy (NSOM) to reveal coherences involving a single cesium lead bromide perovskite QD (CsPbBr) at room temperature.

Chemo- and Stereoselective Intermolecular [2+2] Photocycloaddition of Conjugated Dienes using Colloidal Nanocrystal Photocatalysts.

The use of visible-light photosensitizers to power [2+2] photocycloadditions that produce complex tetrasubstituted cyclobutanes is a true success of photochemistry, but the scope of this reaction has been limited to activated , -unsaturated carbonyls. This paper describes selective intermolecular homo- and hetero-[2+2] photocycloadditions of terminal and internal aryl conjugated dienes - substrates historically unsuited for this reaction because of their multiple possible reaction pathways and product configurations - through triplet-triplet energy transfer from CdSe nanocrystal photocatalysts, to generate valuable and elusive aryl vinylcyclobutanes. The negligible singlet-triplet splitting of nanocrystals' excited states allows them to drive the [2+2] pathway over the competing [4+2] photoredox pathway, a chemoselectivity not achievable with any known molecular photosensitizer.

Tunable Broad Light Emission from 3D "Hollow" Bromide Perovskites through Defect Engineering.

Hybrid halide perovskites consisting of corner-sharing metal halide octahedra and small cuboctahedral cages filled with counter cations have proven to be prominent candidates for many high-performance optoelectronic devices. The stability limits of their three-dimensional perovskite framework are defined by the size range of the cations present in the cages of the structure. In some cases, the stability of the perovskite-type structure can be extended even when the counterions violate the size and shape requirements, as is the case in the so-called "hollow" perovskites.