The [2+2] cycloaddition-retroelectrocyclization (CA-RE) reaction between electron-rich alkynes and electron-deficient alkenes is an efficient procedure to create nonplanar donor-acceptor (D-A) chromophores in both molecular and polymeric platforms. They feature attractive properties including intramolecular charge-transfer (ICT) bands, nonlinear optical properties, and redox activities for use in next-generation electronic and optoelectronic devices. This Review summarizes the development of the CA-RE reaction, starting from the initial reports with organometallic compounds to the extension to purely organic systems. The structural requirements for rapid, high-yielding transformations with true click chemistry character are illustrated by examples that include the broad alkyne and alkene substitution modes. The CA-RE click reaction has been successfully applied to polymer synthesis, with the resulting polymeric push-pull chromophores finding many interesting applications.

The [2+2] Cycloaddition-Retroelectrocyclization (CA-RE) Click Reaction: Facile Access to Molecular and Polymeric Push-Pull Chromophores.

Third-order nonlinear optical properties of cyanine dyes with click chemistry modification

The synthesis and characterization of four new tetracyanobutadiene (TCBD) derivatives (1-3 and 2') incorporating 2- or 2,7-fluorenyl and diphenylamino moieties are reported. The electroactivity of 1-3 and 2' was studied by cyclic voltammetry (CV), while the linear optical and (third order) nonlinear optical (NLO) properties were investigated by electronic spectroscopy and Z -scan studies, respectively. All experimental investigations were rationalized by DFT computations, providing an insight into the electronic structure of these derivatives and on their application potential. We show that these derivatives are nonluminescent in solution at ambient temperatures, but become fluorescent in solvent glasses. This finding constitutes an unprecedented observation for TCBD derivatives. Also, we show by Z-scan studies that these derivatives behave as two-photon absorbers in the near-IR range (800-1050 nm). These third-order NLO properties are discussed and compared with those of their alkynyl precursors (4-6), which have been investigated by two-photon excited fluorescence (TPEF).

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Linear Optical and Third-Order Nonlinear Optical Properties of Some Fluorenyl- and Triarylamine-Containing Tetracyanobutadiene Derivatives

The possibility of developing new advanced optical limiters of laser radiation at 532 nm with low limiting thresholds has been demonstrated on thermally stable phthalocyanine J-type dimeric complexes of Mg, Zn, Cu, Ni, and Co. A new “threshold” model based on radiative transfer phenomena in nonlinear optical media was suggested for the exact definition of nonlinear absorption coefficient β and optical limiting threshold Ic. This model allows the determination of the optical characteristics of the limiter in the same active material with layers of different thicknesses, as well as the use of different parameters of laser radiation, such as cross-sectional spatial profiles of the laser beam and shapes of the laser pulse over time. The maximum value of the nonlinear absorption coefficient (β = 360 cm GW−1) and the lowest limiting threshold (Ic = 0.03 J cm−2) were estimated for a J-type zinc phthalocyanine dimer.

Thermally stable J-type phthalocyanine dimers as new non-linear absorbers for low-threshold optical limiters

Nonlinear optical properties of the novel kind of organic donor-acceptor thiophene derivatives with click chemistry modification

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.

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/open.201500124

Lian Yu

Papers

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