Single Molecular Persistent Room-Temperature Phosphorescence and Circularly Polarized Luminescence from Binaphthol-Decorated Optically Innocent Cyclotriphosphazenes.

Circularly polarized luminescence (CPL) features of BINOL-decorated cyclotriphosphazenes (CPs) are reported for the first time. The luminescence dissymmetry factor (glum ) of these compounds in chloroform solutions and polymethyl methacrylate (PMMA) thin films with wt 1 % doping concentrations are found to be 1.0×10-3 , and 2.9×10-3 , respectively. However, no CPL signal is observed for the pristine solids. The enantiomers (CP-(R)/CP-(S)) show ultraviolet photoluminescence (~350-360 nm) in solution and the solid state. These compounds show ~10 times larger absolute photoluminescence quantum yield (PLQY) than the simple BINOLs in the solutions state. In the solid state, CP-(R) shows larger PLQY than binaphthol-(R); in contrast, the S enantiomer shows lower PLQY than binaphthol-(S); this indicates that the isomer-dependent solid-state packing of these compounds plays a crucial role in controlling the PL. Thin films with more than 1 % doping concentration and pristine solids of these compounds do not show persistent room-temperature phosphorescence (pRTP) due to concentration-caused quenching. However, thin films with wt 1 % of these chiral emitters exhibit pRTP characteristics with a ~159-343 ms lifetime under vacuum. Theoretical calculations reveal that the cyclophosphazene acts as an optically innocent dendritic core, and the optical features of these compounds are dictated by the pendent BINOL chromophore.

Crystallization induced room-temperature phosphorescence and chiral photoluminescence properties of phosphoramides.

We report the design and synthesis of a series of room temperature phosphorescent phosphoramides TPTZPO, TPTZPS, and TPTZPSe with a donor (phenothiazine)-acceptor (P = X, X = O, S, and Se) architecture. All the compounds show structureless fluorescence with a nanosecond lifetime in dilute solutions. However, these compounds show dual fluorescence and room temperature phosphorescence (RTP) in the solid state. Both the intensity and energy of luminescence depend on the heteroatom attached to the phosphorus center. For example, compound TPTZPO with the P[double bond, length as m-dash]O unit exhibits fluorescence at a higher energy region than TPTZPS and TPTZPSe with the P[double bond, length as m-dash]S and P[double bond, length as m-dash]Se groups, respectively. Crystalline samples of TPTZPO, TPTZPS, and TPTZPSe show stronger RTP than the amorphous powder of respective compounds. Detailed steady-state, time-resolved photoluminescence and computational studies established that the 3n-π* state dominated by the phenothiazine moiety is the emissive state of these compounds. Although TPTZPS and TPTZPSe crystallized in the chiral space group, only TPTZPSe showed chiroptical properties in the solid state. The luminescence dissymmetry factor (g lum) value of TPTZPS is small and below the detection limit, and a CPL spectrum could not be observed for this compound.

Synthesis and Characterization of Far-Red Emissive Boron-Based Triads Showing Large Stokes Shifts: Optical, TRANES, and Electrochemical Studies.

Herein, we report the design and synthesis of far-red emissive boryl-thiophene-BODIPY triads 1-3. The π-conjugation length and electronic communication between borane and BODIPY moieties are tuned by judiciously varying the size of the oligothiophene spacer in these triads (1, terthiophene; 2, quarterthiophene; and 3, pentathiophene). Conjugates 1-3 showed intriguing triple emissions in the blue to far-red regions. Detailed optical, time-resolved decay kinetics, time-resolved area-normalized emission spectra (TRANES), fluoride binding, and computational studies suggest that the multiple emissions in these triads are due to an inefficient transfer of energy from the boryl-oligothiophene to the BODIPY unit. In addition, all of the conjugates showed a ratiometric fluorescence response to fluoride ions.

Optical temperature sensing by tuning photoluminescence in a wide (visible to near infrared) wavelength range in a Eu3+-doped Bi-based relaxor ferroelectric.

The prevalent material design principles for optical thermometry primarily rely on thermally driven changes in the relative intensities of the thermally coupled levels (TCLs) of rare-earth-doped phosphor materials, where the maximum achievable sensitivity is limited by the energy gap between the TCLs. In this work, a new, to the best of our knowledge, approach to thermometric material design is proposed, which is based on temperature tuning of PL emission from the visible to the NIR region. We demonstrate a model ferroelectric phosphor, Eu3+-doped 0.94(Na1/2Bi1/2TiO3)-0.06(BaTiO3) (NBT-6BT), which, by virtue of the contrasting effects of temperature on PL signals from the host and Eu3+ intraband transitions, can achieve a relative thermal sensitivity as high as 3.05% K-1. This model system provides a promising alternative route for developing self-referencing optical thermometers with high thermal sensitivity and good signal discriminability.

Delayed Fluorescence, Room Temperature Phosphorescence, and Mechanofluorochromic Naphthalimides: Differential Imaging of Normoxia and Hypoxia Live Cancer Cells.

We study the effect of molecular conformation on the electronic coupling between the donor amines and acceptor 1,8-naphthalimide (NPI) in a series of D-A systems 1-4 (A = NPI; D = phenothiazine, phenoxazine, carbazole, diphenylamine, respectively, for 1, 2, 3, and 4). Weakly coupled systems show dual emission in the solution state, while strongly coupled systems show single emission bands. The energy of transitions and photoluminescence (PL) quantum yield are sensitive to the molecular conformation and donor strength. These compounds show delayed emission in the solutions and aggregated state and phosphorescence in the solid state. Compounds 3 and 4 with weak donors exhibit intermolecular slipped π···π interactions in the solid state and consequently exhibit dual (intra- and inter-) phosphorescence at low temperature. Steady state and time-resolved PL studies at variable temperature together with computational and crystal structure analysis were used to rationalize the optical properties of these compounds. The delayed emission of these compounds is sensitive to molecular oxygen; accordingly, these molecules are utilized for differential imaging of normoxia and hypoxia cancer cells.