Covalent organic frameworks (COFs) have garnered immense scientific interest among porous materials because of their structural tunability and diverse properties. However,the response of such materials towardlaser-induced nonlinear optical (NLO) applications is hardly understood and demands prompt attention. Three novel regioregular porphyrin (Por)-based porous COFs-Por-COF-HH and its dual metalated congeners Por-COF-ZnCu and Por-COF-ZnNi-have been prepared and present excellent NLO properties.N otably,i ntensity-dependent NLO switching behavior was observed for these Por-COFs,w hichi sh ighly desirable for optical switching and optical limiting devices. Moreover,t he efficient p-conjugation and charge-transfer transition in ZnCu-Por-COF enabled ahigh nonlinear absorption coefficient (b = 4470 cm/GW) and figure of merit (FOM = s 1 /s o ,3565) value compared to other state-of-the-art materials, including molecular porphyrins (b % 100-400 cm/GW), metalorganic frameworks (MOFs; b % 0.3-0.5 cm/GW), and graphene (b = 900 cm/GW). Molecules/materialswithinherentnonlinearoptical(NLO)properties have profound importance in telecommunications, data storage,d isplay technologies,s ensors,a nd biomedical devices. [1] In this regard, molecular porphyrins have been widely studied because of their versatile optical and electrochemical properties,large and fast NLO responses,possibility of incorporating aw ide range of metals,a nd their good thermochemical stabilities for optical limiting and optical switching applications. [2] Nonetheless,t oenhance and tune optical nonlinearities of singular porphyrin moieties,b athochromic shifting of their absorption bands by large p-electron delocalization is crucial, which becomes possible through de novo design of integrated porphyrin units featuring extended p-conjugation. [3, 4] Along this line,w ep ropose ap orphyrin-linked covalent organic framework (COF) [5] as model system, wherein enhancement and switching of the NLO response can be studied by manipulation of the framework. Among the recognized crystalline materials, COFs are known for being mechanically robust and offering ahighly accessible surface area. Thestructural and electronic tunability of COFs have garnered particular interest in research areas such as adsorption/storage, [6] chemical sensors, [7] electronics, [8] and catalysis. [9] Despite such potential, COFs comprising porphyrin units have not been explored as NLO materials.F or this purpose,aregioregular ordering of multiple metal centers in ac rystalline 2D porphyrin framework-preferably without ap ost-synthetic modification-is desirable.T his challenging objective [10] has great potential in optoelectronics and photo/electrocatalysis applications.Herein, we present aconjugated imine-linked porphyrinhomopolymeric COF (Por-COF-HH; Figure 1a)prepared by Schiff base A4B4 condensation of 5,10,15,20-tetrakis(4-formylphenyl)-21H,23H-porphyrin (TFPP) and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin (TAPP). Adopting the same pathway,w ea lso synthesized regioregular...

We report a porous thiazolo[5,4-d]thiazole-bridged porphyrin organic framework, Por-TzTz-POF, with promising nonlinear optical (NLO) activity.

Covalent organic frameworks (COFs) have garnered immense scientific interest among porous materials because of their structural tunability and diverse properties. However,the response of such materials towardlaser-induced nonlinear optical (NLO) applications is hardly understood and demands prompt attention. Three novel regioregular porphyrin (Por)-based porous COFs-Por-COF-HH and its dual metalated congeners Por-COF-ZnCu and Por-COF-ZnNi-have been prepared and present excellent NLO properties.N otably,i ntensity-dependent NLO switching behavior was observed for these Por-COFs,w hichi sh ighly desirable for optical switching and optical limiting devices. Moreover,t he efficient p-conjugation and charge-transfer transition in ZnCu-Por-COF enabled ahigh nonlinear absorption coefficient (b = 4470 cm/GW) and figure of merit (FOM = s 1 /s o ,3565) value compared to other state-of-the-art materials, including molecular porphyrins (b % 100-400 cm/GW), metalorganic frameworks (MOFs; b % 0.3-0.5 cm/GW), and graphene (b = 900 cm/GW). Molecules/materialswithinherentnonlinearoptical(NLO)properties have profound importance in telecommunications, data storage,d isplay technologies,s ensors,a nd biomedical devices. [1] In this regard, molecular porphyrins have been widely studied because of their versatile optical and electrochemical properties,large and fast NLO responses,possibility of incorporating aw ide range of metals,a nd their good thermochemical stabilities for optical limiting and optical switching applications. [2] Nonetheless,t oenhance and tune optical nonlinearities of singular porphyrin moieties,b athochromic shifting of their absorption bands by large p-electron delocalization is crucial, which becomes possible through de novo design of integrated porphyrin units featuring extended p-conjugation. [3, 4] Along this line,w ep ropose ap orphyrin-linked covalent organic framework (COF) [5] as model system, wherein enhancement and switching of the NLO response can be studied by manipulation of the framework. Among the recognized crystalline materials, COFs are known for being mechanically robust and offering ahighly accessible surface area. Thestructural and electronic tunability of COFs have garnered particular interest in research areas such as adsorption/storage, [6] chemical sensors, [7] electronics, [8] and catalysis. [9] Despite such potential, COFs comprising porphyrin units have not been explored as NLO materials.F or this purpose,aregioregular ordering of multiple metal centers in ac rystalline 2D porphyrin framework-preferably without ap ost-synthetic modification-is desirable.T his challenging objective [10] has great potential in optoelectronics and photo/electrocatalysis applications.Herein, we present aconjugated imine-linked porphyrinhomopolymeric COF (Por-COF-HH; Figure 1a)prepared by Schiff base A4B4 condensation of 5,10,15,20-tetrakis(4-formylphenyl)-21H,23H-porphyrin (TFPP) and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin (TAPP). Adopting the same pathway,w ea lso synthesized regioregular...

The more than a century old Sagnac interferometer is put to first of its kind use to generate an achromatic single-charge vortex equivalent to a Laguerre-Gaussian beam possessing orbital angular momentum (OAM). The interference of counter-propagating polychromatic Gaussian beams of beam waist ωλ with correlated linear phase (ϕ 0 ≥ 0.025 λ) and lateral shear (y 0 ≥ 0.05 ωλ) in orthogonal directions is shown to create a vortex phase distribution around the null interference. Using a wavelength-tunable continuous-wave laser the entire range of visible wavelengths is shown to satisfy the condition for vortex generation to achieve a highly stable white-light vortex with excellent propagation integrity. The application capablitiy of the proposed scheme is demonstrated by generating ultrashort optical vortex pulses, its nonlinear frequency conversion and transforming them to vector pulses. We believe that our scheme for generating robust achromatic vortex (implemented with only mirrors and a beam-splitter) pulses in the femtosecond regime, with no conceivable spectral-temporal range and peak-power limitations, can have significant advantages for a variety of applications.

Wavelength-dependent reproducible nano-gratings were produced on a bulk molybdenum surface upon irradiation with femtosecond laser pulses at near normal incidence in ambient air and water environments. The surface morphology of the irradiated surfaces was characterized by field emission scanning electron microscopy. The ripple spacing was observed to decrease by half when the surface was irradiated with the second harmonic of the fundamental 800 nm radiation. Careful choice of the laser parameters such as fluence, scanning speed, polarization and wavelength were observed to be important for the formation of smooth periodic ripples. The mechanism of formation of polarization-dependent periodic ripples is explained based on the interference model. We also demonstrated the use of a laser direct writing technique for the fabrication of periodic subwavelength structures that have potential applications in photonic devices.