Application of Near‐IR Absorption Porphyrin Dyes Derived from Click Chemistry as Third‐Order Nonlinear Optical Materials

Abstract

Recently, third‐order nonlinear properties of porphyrins and porphyrin polymers and coordination compounds have been extensively studied in relation to their use in photomedicine and molecular photonics. A new functionalized porphyrin dye containing electron‐rich alkynes was synthesized and further modified by formal [2+2] click reactions with click reagents tetracyanoethylene (TCNE) and 7, 7, 8, 8‐tetracyanoquinodimethane (TCNQ). The photophysical properties of these porphyrin dyes, as well as the click reaction, were studied by UV/Vis spectroscopy. In particular, third‐order nonlinear optical properties of the dyes, which showed typical d‐π‐A structures, were characterized by Z‐scan techniques. In addition, the self‐assembly properties were investigated through the phase‐exchange method, and highly organized morphologies were observed by scanning electron microscopy (SEM). The effects of the click post‐functionalization on the properties of the porphyrins were studied, and these functionalized porphyrin dyes represent an interesting set of candidates for optoelectronic device components.

Synthesis and Properties of New Multiple TCNE Adducts from Dialkynyl‐N‐(het)arylpyrroles

“…Dipolar chromophores have been extensively studied due to their wide range of applications in diverse fields such as in OLED devices,, organic photovoltaic cells, and non‐linear optics . These particular chromophores are push–pull conjugated molecules consisting of electron donor (D) and electron acceptor (A) groups connected through a conjugated π‐bridge.…”

Butterfly‐Shaped Thiophene‐Pyridine Hybrids: Green Electroluminescence and Large Third‐Order Optical Nonlinearities

“…Zhang et al [46] studied the NLO and optical limiting properties of graphene oxide-Fe 3 O 4 hybrid material, which showed an enhanced β eff of 2.6 × 10 À 10 m W À 1 with the LT of 2.82 J cm À 2 , whereas new quinoxaline based push-pull molecule with 1,3-indandione as acceptor was synthesized and its third-order NLO properties were studied by Gopi et al, [47] which showed an effective TPA with very high β eff of 2.0 × 10 À 10 m W À 1 and low LT of 1.15 J cm À 2 . Further, Mi et al [48] synthesized Zn-complexed D-π-A type porphyrin derivative, PorÀ ZnÀ N, through [2 + 2] click reactions and studied the NLO response of the material, which showed RSA with β eff of 4.8 × 10 À 10 m W À 1 . Specifically, 2TPA-TPY and 2CBZ-TPY of the present study having similar structural arrangement as that of our previously reported molecules wherein the same core structure (i. e., TPY) was connected to small end groups such as thiophene/phenyl acrylonitriles, [44] show enhanced NLO properties compared to the previous molecules.…”

Click Chemistry ‐ Inspired Synthesis of Porphyrin Hybrid Glycodendrimers as Fluorescent Sensor for Cu(II) Ions

“…[5] Furthermore, a wide range of porphyrin analogues has also been explored as chemical sensor, [6] which have diverse applications for the surface potential, [7] photomedicine, [8] electrical conductivity, [9] molecular switches, [10] and optical absorbance. [11] Interestingly, metalloporphyrin arrays have been effectively used as sensors for an artificial olfaction via 'Smell-Seeing' method. [12] In addition, photodynamic therapy, a noninvasive therapeutic tool for the cancer treatment using this interesting scaffold has been extensively studied in the recent years.…”