β-Octakis(methylthio)porphycenes: synthesis, characterisation and third order nonlinear optical studies

Abstract

A novel electron deficient β-octakis(methylthio)porphycene, along with its Zn(ii) and Ni(ii) derivatives, was synthesized for the first time. The macrocyclic structure exhibits core ruffling with a largely red shifted absorption band (∼750 nm) and also a large enhancement in the third order nonlinear optical response.

Gram-scale synthesis of porphycenes through acid-catalyzed oxidative macrocyclizations of E/Z-mixed 5,6-diaryldipyrroethenes

“…13,14 Various porphycenes with meso-and b-substituents and their metal complexes have been reported to have tunable functionalities, crystallinities and solubilities. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] However, the main obstacle to the widespread application of porphycenes is the lack of efficient and economical methods for their production. Therefore, porphycene chemistry has advanced more slowly than that of the parent isomer porphyrin.…”

β‐Octamethoxy‐Substituted 22π and 26π Stretched Porphycenes: Synthesis, Characterization, Photodynamics, and Nonlinear Optical Studies

“…We can see that acetylene–cumulene porphyrinoids are much rigid and tend to be more effectively conjugated than [22]porphyrins‐(2.2.2.2) with a vinylinic linker, which is known to undergo an isodynamic transformation involving rotation around trans CHCH bonds4 and lead to a relatively low TPA cross section. Interestingly, expansion of the aromaticity could be clearly observed for all expanded porphycenes as evident from their higher TPA cross section values compared with their porphycene analogues 6e…”

Nonlinear optical properties of rhenium(I) complexes: Influence of the extended π-conjugated connectors and proton abstraction

“…Because they exhibit large and fast NLO activities by charge-transfer transitions between the metal and ligands [5][6][7][8]. The transition metal complexes Ru (II), Fe (II), Pt (II), Re (I) and Ni (II) have shown versatile second-order NLO properties [9][10][11][12][13]. For example, Ordronneau et al have reported that the β value of the Re (I) dithienylethene complex increases about 5-fold through reversible photoisomerization process, which achieves a switchable NLO response [14].…”