Large Nonlinear Optical Activity of a Near-infrared-absorbing Bithiophene-based Polymer with a Head-to-head Linkage.

Although the production of near-infrared (NIR)-absorbing organic polymers with an excellent nonlinear optical (NLO) response is vital for various optoelectronic devices and photodynamic therapy, the molecular design and relevant photophysical investigation still remain challenging. In this work, large NLO activity is observed for an NIR-absorbing bithiophene-based polymer with a unique head-to-head linkage in the NIR region. The saturable absorption coefficient and modulation depth of the polymer are determined as ∼-3.5×105  cm GW-1 and ∼32.43%, respectively. Notably, the polymer exhibits an intrinsic nonlinear refraction index up to ∼-9.36 cm2 GW-1 , which is six orders of magnitude larger than that of CS2 . The maximum molar-mass normalized two-photon absorption cross-section (σ2 /M) of this polymer can be up to ∼14 GM at 1200 nm. Femtosecond transient absorption measurements reveal significant spectral overlap between the 2PA and excited state absorption in the 1000-1400 nm wavelength range and an efficient triplet quantum yield of ∼36.7%. The results of this study imply that this NIR-absorbing polymer is promising for relevant applications.

2.8 µm passively Q-switched Er:ZBLAN fiber laser with an Sb saturable absorber mirror.

A Q-switched Er:ZBLAN fiber laser operating at 2.8 µm was realized by employing Sb as the saturable material. The Sb material was deposited on a gold mirror by the magnetron-sputtering deposition method to develop a saturable absorber mirror (SAM). By employing the Sb-SAM in an Er:ZBLAN fiber laser, stable Q-switching operation was achieved at central wavelength of 2799.7 nm with the repetition rates ranging from 33.3 to 58.8 kHz and the pulse duration ranging from 5.7 to 1.7 µs. The Sb-SAM still works stably under the maximum pump power of 5.6 W, with an output power of 59 mW corresponding to the pulse energy of 1.03 µJ. To our knowledge, this was the first demonstration of Sb-based saturable material in Er:ZBLAN fiber laser for mid-infrared Q-switched pulse generation operating in the 2.8 µm regime, indicating its potential applications in the mid-infrared waveband.

Water-soluble chiral tetrazine derivatives: towards the application of circularly polarized luminescence from upper-excited states to photodynamic therapy.

A new family of water-soluble chiral tetrazine derivatives 1 and 2 is reported. Spectroscopic studies reveal that the derivatives violate Kasha's rule and emit from their upper-excited states (S n , n > 1). The transition assignments are supported by time-dependent density functional theory calculations. More importantly, both chromophores exhibit anisotropy factors on the order of ∼10-3 to 10-4 for circular dichroism and circularly polarized luminescence (CPL) from upper-excited states. Additionally, the nonplanar geometry of the derivatives induces a significant yield of triplet excited states. Transient absorption spectroscopic measurements reveal high triplet quantum yields of ∼86% for 1 and ∼81% for 2. Through in vitro studies, we demonstrate that the derivatives can be used as photodynamic therapy (PDT) agents, providing a highly efficient form of cancer therapy. This study is the first demonstration of simple organic molecules with CPL from upper-excited states and efficient PDT.

Nitric oxide activatable photosensitizer accompanying extremely elevated two-photon absorption for efficient fluorescence imaging and photodynamic therapy.

Elevated nitric oxide (NO) levels perform an important pathological role in various inflammatory diseases. Developing NO-activatable theranostic materials with a two-photon excitation (TPE) feature is highly promising for precision imaging and therapy, but constructing such materials is still a tremendous challenge. Here, we present the first example of a NO-activatable fluorescent photosensitizer (DBB-NO) accompanying extremely NO-elevated two-photon absorption (TPA) for efficient fluorescence imaging and photodynamic therapy (PDT). Upon responding to NO, DBB-NO shows not only a remarkably enhanced fluorescence quantum yield (ΦF, 0.17% vs. 9.3%) and singlet oxygen quantum yield (ΦΔ, 1.2% vs. 82%) but also an extremely elevated TPA cross-section (δ, 270 vs. 2800 GM). Simultaneous enhancement of ΦΔ, ΦF and δ allows unprecedented two-photon fluorescence brightness (δ × ΦF = 260.4 GM) and two-photon PDT (TP-PDT) efficiency (δ × ΦΔ = 2296 GM) which precedes the value for a commercial two-photon photosensitizer by two orders of magnitude. With these merits, the proof-of-concept applications of NO-activatable two-photon fluorescence imaging and TP-PDT in activated macrophages (in which NO is overproduced) were readily realized. This work may open up many opportunities for constructing two-photon theranostic materials with other pathological condition-activatable features for precise theranostics.

Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation.

The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT.