Porous shape-persistent rylene imine cages with tunable optoelectronic properties and delayed fluorescence

A simultaneous combination of porosity and tunable optoelectronic properties, common in covalent organic frameworks, is rare in shape-persistent organic cages. Yet, organic cages offer important molecular advantages such as solubility and modularity. Herein, we report the synthesis of a series of chiral imine organic cages with three built-in rylene units by means of dynamic imine chemistry and we investigate their textural and optoelectronic properties. Thereby we demonstrate that the synthesized rylene cages can be reversibly reduced at accessible potentials, absorb from UV up to green light, are porous, and preferentially adsorb CO₂ over N₂ and CH₄ with a good selectivity. In addition, we discovered that the cage incorporating three perylene-3,4:9,10-bis(dicarboximide) units displays an efficient delayed fluorescence. Time-correlated single photon counting and transient absorption spectroscopy measurements suggest that the delayed fluorescence is likely a consequence of a reversible intracage charge-separation event. Rylene cages thus offer a promising platform that allows combining the porosity of processable materials and photochemical phenomena useful in diverse applications such as photocatalysis or energy storage.

Chiral rylene imine cages combine porosity and tunable optoelectronic properties. They adsorb CO₂ over N₂ with good selectivity and can show an efficient delayed fluorescence.     

Synthesis and characterization of two new aryl cyclobutyl ketoethyl methacrylate monomers and their polymers

Two new methacrylate monomers, 2‐[3‐(6‐tetralino)‐3‐methylcyclobutyl]‐2‐ketoethyl methacrylate (TKEMA) and 2‐(3‐mesityl‐3‐methylcyclobutyl)‐2‐ketoethyl methacrylate (MKEMA), were obtained from the reaction of 1‐chloroacetyl‐3‐methyl‐3‐arylcyclobutane with sodium methacrylate. The oxime and hydrazone derivatives of poly(TKEMA) and poly(MKEMA) were prepared with hydroxylamine and 2,4‐dinitrophenyl hydrazine. Poly(TKEMA) and poly(MKEMA), their oxime and hydrazone derivatives, and the monomers were characterized with Fourier transform infrared and NMR techniques. The glass‐transition temperatures and thermal stability of the polymers and their oxime and hydrazone derivatives were compared. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4167–4173, 2001     

Coherence enhancement of spatially incoherent light beams through soliton interactions

We show that the spatial coherence of a partially incoherent light beam can be greatly enhanced through an energy-conserving interaction with an incoherent or a coherent dark spatial soliton. Computer simulations show that during this process a portion of the incoherent beam is trapped within the dark notch of the dark soliton, thus forming a sharp intensity spike. In this region the correlation length dramatically increases by at least 2 orders of magnitude.     

Modulation instability of incoherent beams in noninstantaneous nonlinear media

We show that modulation instability can exist with partially spatially incoherent light beams in a noninstantaneous nonlinear environment. For such incoherent modulation instability to occur, the value of the nonlinearity has to exceed a threshold imposed by the degree of spatial coherence.     

Extremal effective divisors on \overline{\mathcal M}_{1,n}

For every \(n\ge 3\) , we exhibit infinitely many extremal effective divisors on \(\overline{\mathcal M}_{1,n}\) , the Deligne-Mumford moduli space parameterizing stable genus one curves with \(n\) ordered marked points.     

Direct imaging of localized surface plasmon polaritons

In this Letter, we report on dark field imaging of localized surface plasmon polaritons (SPPs) in plasmonic waveguiding bands formed by plasmonic coupled cavities. We image the light scattered from SPPs in the plasmonic cavities excited by a tunable light source. Tuning the excitation wavelength, we measure the localization and dispersion of the plasmonic cavity mode. Dark field imaging has been achieved in the Kretschmann configuration using a supercontinuum white-light laser equipped with an acoustooptic tunable filter. Polarization dependent spectroscopic reflection and dark field imaging measurements are correlated and found to be in agreement with finite-difference time-domain calculations.     

A multistate switchable [3]rotacatenane

Rotacatenanes are exotic molecular compounds that can be visualized as a unique combination of a [2]catenane and a [2]rotaxane, thereby combining both the circumrotation of the ring component (rotary motion) and the shuttling of the dumbbell component (translational motion) in one structure. Herein, we describe a strategy for the synthesis of a new switchable [3]rotacatenane and the investigation of its switching properties, which rely on the formation of tetrathiafulvalene (TTF) radical π-dimer interactions-namely, the mixed-valence state (TTF(2) )(+.) and the radical-cation dimer state (TTF(+.) )(2) -under ambient conditions. A template-directed approach, based on donor-acceptor interactions, has been developed, resulting in an improved yield of the key precursor [2]catenane, prior to rotacatenation. The nature of the binding between the [2]catenane and selected π-electron-rich templates has been elucidated by using X-ray crystallography and UV/Vis spectroscopy as well as isothermal titration microcalorimetry. The multistate switching mechanism of the [3]rotacatenane has been demonstrated by cyclic voltammetry and EPR spectroscopy. Most notably, the radical-cation dimer state (TTF(+.) )(2) has been shown to enter into an equilibrium by forming the co-conformation in which the two 1,5-dioxynaphthalene (DNP) units co-occupy the cavity of tetracationic cyclophane, thus enforcing the separation of TTF radical-cation dimer (TTF(+.) )(2) . The population ratio of this equilibrium state was found to be 1:1. We believe that this research demonstrates the power of constructing complex molecular machines using template-directed protocols, enabling us to make the transition from simple molecular switches to their multistate variants for enhancing information storage in molecular electronic devices.     

Wide-field lensless fluorescent microscopy using a tapered fiber-optic faceplate on a chip

We demonstrate lensless fluorescent microscopy over a large field-of-view of ~60 mm(2) with a spatial resolution of <4 μm. In this on-chip fluorescent imaging modality, the samples are placed on a fiber-optic faceplate that is tapered such that the density of the fiber-optic waveguides on the top facet is >5 fold larger than the bottom one. Placed on this tapered faceplate, the fluorescent samples are pumped from the side through a glass hemisphere interface. After excitation of the samples, the pump light is rejected through total internal reflection that occurs at the bottom facet of the sample substrate. The fluorescent emission from the sample is then collected by the smaller end of the tapered faceplate and is delivered to an opto-electronic sensor-array to be digitally sampled. Using a compressive sampling algorithm, we decode these raw lensfree images to validate the resolution (<4 μm) of this on-chip fluorescent imaging platform using microparticles as well as labeled Giardia muris cysts. This wide-field lensfree fluorescent microscopy platform, being compact and high-throughput, might provide a valuable tool especially for cytometry, rare cell analysis (involving large area microfluidic systems) as well as for microarray imaging applications.