Fused porphyrinoids as promising near-infrared absorbing dyes

Abstract

Various aromatic segments have been fused onto the porphyrin periphery to create porphyrinoids that have expanded p-conjugated networks and thus exhibit red-shifted absorption spectra. Fused coplanar porphyrin oligomers, represented by meso-meso, b-b, b-b triply linked porphyrin arrays (porphyrin tapes), are endued with more red-shifted absorption spectra and better nonlinear optical properties.These fused porphyrinoids have emerged as promising near-infrared (NIR) absorbing dyes, pointing to future applications such as conducting wire, NIR emitter, photovoltaics, and nonlinear optical materials.Developments of the fused porphyrinoid chemistry are reviewed in this feature article with focus on the synthesis, the relationships between their absorption spectra and molecular structures, and the applications in materials science.

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

“…Other routes that have been investigated for introduction of exocyclic rings have been reviewed. 372,375–378 Each of these routes has certain attractions; however, none appeared compatible with the synthetic route to chlorins wherein Eastern and Western halves are joined in a rational manner.…”

Highly efficient synthesis of novel methyl 132-methylene mesopyropheophorbide a and its stereoselective Michael addition reaction

“…[15][16][17] Among them, methyl 13 2 -oxopyropheophorbide a containing a bifunctional cyclopentanedione ring system is particularly important because it is the unique precursor till now to prepare verdinochlorins 18,19 and construct polyaromatic ring systems such as quinoxaline, benzimidazole and perimidine fused with the chromophore of (bacterio)chlorophylls. [23][24][25] Unfortunately further studies of aromatic ring fused chlorophylls have been limited due to the lack of suitable reactive positions. [23][24][25] Unfortunately further studies of aromatic ring fused chlorophylls have been limited due to the lack of suitable reactive positions.…”

Electrochemistry and spectroelectrochemistry of metallohexaphyrins containing bis-copper or bis-zinc central metal ions

“…Expanded porphyrins have attracted considerable attention, in part because of their large conjugated p-system and flexible conformation leading to unique spectral, electrochemical and coordination properties , and in part they have wide potential applications in the fields of functional materials, molecular wires and near-infrared dyes [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45]. Hexaphyrins are an example of expanded porphyrins which contain six pyrrole rings in the macrocycle and possess a sufficiently large porphyrin cavity to allow for the coordination of two metal ions and the formation of dinuclear metal complexes.…”