Estimating Phosphorescent Emission Energies in Ir Complexes Using Large-Scale Quantum Computing Simulations.

Here we calculate T →S transition energies in nine phosphorescent iridium complexes using the iterative qubit coupled cluster (iQCC) method to determine if quantum simulations have any advantages over classical methods. These simulations would require a gate-based quantum computer with at least 72 fully-connected logical qubits. Since such devices do not yet exist, we demonstrate the iQCC method using a purpose-built quantum simulator on classical hardware.

Red-Emissive Cell-Penetrating Polymer Dots Exhibiting Thermally Activated Delayed Fluorescence for Cellular Imaging.

Fluorescence imaging in living cells is key to understanding many biological processes, yet autofluorescence from the sample can lower sensitivity and hinder high-resolution imaging. Time-gated measurements using phosphorescent metal complexes can improve imaging, at the cost of potential toxicity from the use of heavy metals. Here, we describe orange/red-emitting polymer dots (Pdots) exhibiting thermally activated delayed fluorescence (TADF) for time-gated imaging.

Near-Infrared-Emitting Boron-Difluoride-Curcuminoid-Based Polymers Exhibiting Thermally Activated Delayed Fluorescence as Biological Imaging Probes.

Near-infrared-emitting polymers were prepared using four boron-difluoride-curcuminoid-based monomers using ring-opening metathesis polymerization (ROMP). Well-defined polymers with molecular weights of ≈20 kDa and dispersities <1.07 were produced and exhibited near-infrared (NIR) emission in solution and in the solid state with photoluminescence quantum yields (Φ ) as high as 0.

Thermally Assisted Fluorescent Polymers: Polycyclic Aromatic Materials for High Color Purity and White-Light Emission.

Thermally activated delayed fluorescence (TADF) sensitization of fluorescence is a promising strategy to improve the color purity and operational lifetime of conventional TADF organic light-emitting diodes (OLEDs). Here, we propose a new design strategy for TADF-sensitized fluorescence based on acrylic polymers with a pendant energy-harvesting host, a TADF sensitizer, and fluorescent emitter monomers. Fluorescent emitters were rationally designed from a series of homologous polycyclic aromatic amines, resulting in efficient and color-pure polymeric fluorophores capable of harvesting both singlet and triplet excitons.

1,8-Naphthalimide-Based Polymers Exhibiting Deep-Red Thermally Activated Delayed Fluorescence and Their Application in Ratiometric Temperature Sensing.

A series of naphthalimide (NAI)-based red-emissive thermally activated delayed fluorescence (TADF) acrylic monomers has been designed and synthesized. When copolymerized with a host material by Cu(0)-reversible deactivation radical polymerization (Cu(0)-RDRP), polymers exhibiting orange to deep-red TADF were obtained with quantum yields of up to 58% in solution and 31% in the solid state. These emitters exhibit dual emission consisting of high-energy prompt fluorescence from the NAI acceptor (λ = 340 nm in toluene) and red-delayed fluorescence from the charge-transfer process (λ = 633-711 nm in toluene).

Color-Tunable Thermally Activated Delayed Fluorescence in Oxadiazole-Based Acrylic Copolymers: Photophysical Properties and Applications in Ratiometric Oxygen Sensing.

Polymer-based emitters are a promising route to the production of low-cost, scalable solution-processable luminescent materials. Here we describe a series of acrylic oxadiazole-based donor-acceptor monomers with tunable emission from blue to orange, with quantum yields as high as 96%. By introducing structural constraints that limit donor-acceptor orbital overlap, thermally activated delayed fluorescence (TADF) was observed in these materials.

Structurally versatile phosphine and amine donors constructed from N-heterocyclic olefin units.

A general strategy for the synthesis of hindered N- and P-based donors is presented whereby the strongly electron releasing N-heterocyclic olefin (NHO) unit, IPr[double bond, length as m-dash]CH-, (IPr[double bond, length as m-dash]CH- = [(HCNDipp)2C[double bond, length as m-dash]CH](-); Dipp = 3,6-(i)Pr2C6H2) is linked to terminally bound phosphine and amine donors. Preliminary coordination chemistry is presented involving phosphine (IPr[double bond, length as m-dash]CH)PR2 (R = (i)Pr and Ph) and amine (IPr[double bond, length as m-dash]CH)NMe2 ligands and the Lewis acids BH3 and AuCl. Interestingly, (IPr[double bond, length as m-dash]CH)NMe2 binds AuCl through an exocyclic olefin unit, while the softer phosphorus centers in (IPr[double bond, length as m-dash]CH)PR2 coordinate to yield Au-P linkages; thus the reported NHO-based ligands exhibit tunable binding modes to metals.

Metal-Free Dehydrogenation of Amine-Boranes by Tunable N-Heterocyclic Iminoboranes.

We report the synthesis of structurally tunable boron complexes supported by N-heterocyclic imine ligands IPr=N-BR (IPr=[(HCNDipp) C], Dipp=2,6-iPr C H , R=Cl and/or Ph) that have the ability to abstract dihydrogen from amine-boranes, and instigate their dehydrocoupling. In one instance, mild heating of the hydrogen addition product IPr=NH-B(Ph)HCl releases H to regenerate the starting N-heterocyclic iminoborane; accordingly IPr=N-B(Ph)Cl can be used as a metal-free catalyst to promote the dehydrocoupling of MeNH ⋅BH to yield N-methylaminoborane oligomers [MeNH-BH ] .