Fluorescent molecular rotors (FMRs) can act as viscosity sensors in various media including subcellular organelles and microfluidic channels. In FMRs, the rotation of rotators connected to a fluorescent π-conjugated bridge is suppressed by increasing environmental viscosity, resulting in increasing fluorescence (FL) intensity. In this minireview, we describe recently developed FMRs including push-pull type π-conjugated chromophores, meso-phenyl (borondipyrromethene) (BODIPY) derivatives, dioxaborine derivatives, cyanine derivatives, and porphyrin derivatives whose FL mechanism is viscosity-responsive. In addition, FMR design strategies for addressing various issues (e.g., obtaining high FL contrast, internal FL references, and FL intensity-contrast trade-off) and their biological and microfluidic applications are also discussed.
Efficient broadband organic terahertz (THz) generators using X‐shaped alignment of the nonlinear optical chromophores, as an alternative to the parallel alignment of chromophores in benchmark organic crystals, are reported. All the developed six organic benzothiazolium crystals exhibit an isomorphic X‐shaped alignment of chromophores, resulting in an unprecedentedly large off‐diagonal optical nonlinearity (>100 × 10−30 esu), which presents one of the largest off‐diagonal optical nonlinearity of organic crystals. The benzothiazolium crystals exhibit efficient broadband THz wave generation employing the off‐diagonal optical nonlinearity, in contrast to the present state‐of‐the‐art organic THz generators that mostly utilize diagonal optical nonlinearity. For using off‐diagonal and diagonal optical nonlinearities, the polarization of the optical pump is perpendicular and parallel, respectively, to the polar axis of crystals. In addition to a large THz wave generation efficiency with one order of magnitude higher peak‐to‐peak THz electric field than that generated in a 1.0‐mm‐thick inorganic benchmark ZnTe crystal, the benzothiazolium crystals generate broadband THz spectra with an upper cut‐off frequency of near 8 THz, and the absence of strong absorption dimples in the range of 0.5−4 THz. Therefore, the X‐shaped alignment of chromophores presents an interesting potential alternative for efficient broadband organic THz generators.
Enhanced terahertz (THz) wave generation is demonstrated in nonlinear organic crystals through refractive index engineering, which improves phase matching characteristics substantially. Unlike conventional low‐bandgap nonlinear organic crystals, the newly designed benzimidazolium‐based HMI (2‐(4‐hydroxy‐3‐methoxystyryl)‐1,3‐dimethyl‐1H‐benzoimidazol‐3‐ium) chromophore possesses a relatively wide bandgap. This reduces the optical group index in the near‐infrared, allowing better phase matching with the generated THz waves, and leads to high optical‐to‐THz conversion. A unique feature of the HMI‐based crystals, compared to conventional wide‐bandgap aniline‐based crystals, is their remarkably larger macroscopic optical nonlinearity, a one order of magnitude higher diagonal component in macroscopic nonlinear susceptibility than NPP ((1‐(4‐nitrophenyl)pyrrolidin‐2‐yl)methanol) crystals. The HMI‐based crystals also exhibit much higher thermal stability, with a melting temperature Tm above 250 °C, versus aniline‐based crystals (116 °C for NPP). With pumping at the technologically important wavelength of 800 nm, the proposed HMI‐based crystals boost high optical‐to‐THz conversion efficiency, comparable to benchmark low‐bandgap quinolinium crystals with state‐of‐the‐art macroscopic nonlinearity. This performance is due to the excellent phase matching enabled by decreasing optical group indices in the near‐infrared through wide‐bandgap chromophores. The proposed wide‐bandgap design is a promising way to control the refractive index of various nonlinear organic materials for enhanced frequency conversion processes.
New molecular salt crystals based on linear‐shaped polymer‐like cation–anion assembly exhibiting extremely large nonlinear optical response and high THz generation efficiency are reported. Two hydroxy benzothialzolium PMB (2‐(4‐(4‐(hydroxymethyl)piperidin‐1‐yl)styryl)‐3‐methylbenzo[d]thiazol‐3‐ium) crystals with different benzenesulfonate counter anions provide isomorphic crystal structure with acentric monoclinic Cc space group symmetry. In contrast to previously reported benchmark nonlinear optical salt crystals with a parallel‐type cation–anion assembly, newly developed PMB‐based crystals exhibit a series‐type cation–anion assembly mediated by strong bidentate‐like hydrogen‐bonds. Such series‐type cation–anion assembly results in perfect alignment of highly nonlinear PMB cations in the crystalline state, leading to extremely large diagonal component of the second‐order nonlinear optical coefficient exceeding that of the state‐of‐the‐art nonlinear optical crystals. In THz wave generation experiments based on optical rectification, a 0.33 mm thick PMB crystal generates intense THz pulses with peak‐to‐peak THz electric field of 430 kV cm−1 and extremely broad flat spectrum with upper cut‐off frequency of above 8.0 THz. In addition, compared to inorganic standard 1.0 mm thick ZnTe crystals, the PMB crystal delivers a 24 times higher THz electric field and about 3 times broader bandwidth. Therefore, hydroxy benzothialzolium PMB crystals are highly desired novel materials for various nonlinear optical applications including THz photonics.
Invited for the cover of this issue is the collaborative work of the groups of O‐Pil Kwon (Ajou University), Chang‐Lyoul Lee (Advanced Photonics Research Institute, APRI/Gwangju Institute of Science and Technology, GIST), and Sehoon Kim (Korea Institute of Science and Technology, KIST). The cover image illustrates the viscosity‐sensitive fluorescent behavior of fluorescent molecular rotors (FMRs) in various viscous media. The intensity of the FMRs increases with decreasing speed of the rotor; this is portrayed as the waterwheel in the cover image. When the waterwheel slowly rotates in winter (high viscosity media), FMR—portrayed as the house in the image—shows strong fluorescent‐light illumination (left‐hand side of the image). In contrast, the right‐hand side of image depicts decreasing fluorescence intensity with increasing rotation of the waterwheel (low viscosity media). Read the full text of the article at https://doi.org/10.1002/chem.201801389.
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