Optoelectronic and Self‐assembly Properties of Porphyrin Derivatives with Click Chemistry Modification

Abstract

A series of functionalized porphyrin molecules containing electron-rich alkynes, synthesized by means of the Sonogashira coupling reaction were further modified by reacting the ethynyl groups with click reagent through a formal [2+2] click reaction. The photophysical and electrochemical properties of the porphyrin derivatives were studied by UV/Vis spectroscopy and cyclic voltammetry. We show that the optoelectronic properties are affected by the click reagent groups and central metal ions. The functionalized porphyrin molecules show strong charge-transfer (CT) bands in the visible region (near-IR region) and potent redox activities. Through a phase-exchange self-assembly method, the highly organized morphologies were observed by scanning electron microscopy (SEM). The functionalized porphyrin molecules represent an interesting set of candidates for optoelectronic device components. The effect of the metal ions or click reagent groups on the self-assembly properties were also studied by the UV/Vis spectroscopic titration experiments.

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

“…Figure shows the “open‐aperture” Z‐scan data and the normalized transmittance curves of all products, which could be fitted perfectly with respect to equations reported by references . In Figure a,b, profound transmittance valleys can be seen around the focal plane, which was characteristic of reverse saturable absorption (RSA)‐type behavior of Por−Zn−N and Por−Zn−TCNE .…”

“…Although continuous optimization was explored previously, some porphyrin derivatives were obtained through the fast, high‐yielding, and catalyst‐free [2+2] click reaction, However, very little research has been done on the porphyrin dyes modified by [2+2] click chemistry with high third‐order optical nonlinearities. In particular, innovative [2+2] cycloaddition of strong electron acceptors, such as tetracyanoethene (TCNE) and 7,7,8,8‐tetracyanoquinodimethane (TCNQ), to electron‐rich alkynes provides efficient access to nonplanar push–pull chromophores featuring intense intramolecular charge‐transfer (CT) and optical properties …”

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

“…Alkynes substituted by boron dipyrromethene (BODIPY) and p-methoxyphenyl groups at the two ends underwent aC A-RE reaction with TCNE at 20 8 8Ct oy ield the TCBD product in moderate to good yields (51-77 %; Table 1, entry 12). [29,30] Recently,a ctivation by donors featuring nitrogen atoms directly attached to the alkyne was found to be quite effective. Both free-base and metalloporphyrins (Zn or Cu), as well as chlorophyll derivatives,d isplayed sufficient activity for the reaction to progress at 20 8 8C ( Table 1, entries 13 and 14).…”

“…Both free-base and metalloporphyrins (Zn or Cu), as well as chlorophyll derivatives,d isplayed sufficient activity for the reaction to progress at 20 8 8C ( Table 1, entries 13 and 14). [29,30] Recently,a ctivation by donors featuring nitrogen atoms directly attached to the alkyne was found to be quite effective. 3,3-Diethyl-or diisopropyltriazene groups provided strong activation, allowing for aC A-RE reaction with TCNE at 20 8 8C ( Table 1, entry 15).…”

3-Alkynylindoles as Building Blocks for the Synthesis of Electronically Tunable Indole-Based Push–Pull Chromophores

“… 46 Similarly, long-term storage limitations and instability reduce the diversity of donor-substituted alkynes used in CA-RE. Metal acetylides, 19 , 47 dialkylaniline, 20 ferrocene, 23 thiophene, 48 p-methoxybenzene, 48 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY), 49 cyclopenta[ b ]furan-2-one, 50 metalloporphyrins, 51 carbazole-substituted alkynes, 52 ynamides, 53 tetrathiafulvalene, 17 azulene, 54 phenothiazine, 55 triazene, 56 , 57 and ureas 33 are donor substrates displaying sufficient reactivity in CA-RE reactions with TCNE. Surprisingly, the donor substrate scope (dialkylaniline, 42 ferrocene, 58 cyclopenta[ b ]furan-2-one, 59 carbazole, 60 metal acetylides, 61 azulene, 62 phenothiazine, 63 thiophene 64 ) is much more limited in CA-RE reactions with TCNQ ( Figure 1 ).…”