Similarities and differences between Mn(ii) and Zn(ii) coordination polymers supported by porphyrin-based ligands: synthesis, structures and nonlinear optical properties

Abstract

Four coordination polymers (CPs) Mn-TMPP (1), Zn-TMPP (2), Mn-THPP (3), and Zn-THPP (4) have been synthesized and characterized (H2TMPP = meso-tetrakis (6-methylpyridin-3-yl) porphyrin; H2THPP = meso-tetrakis (6-(hydroxymethyl) pyridin-3-yl) porphyrin). The...

Interpenetrated Metal-Porphyrinic Framework for Enhanced Nonlinear Optical Limiting

“…Recently porphyrin-based MOFs (also called metal-porphyrinic frameworks) with tailorable photo/electric features − have been realized to study their OL performance. Despite some strategies emerging to improve their OL effect by the introduction of tunable metallized porphyrinic ligands, adjusting morphology, and loading guest molecule or doping carbon materials in MOFs, ,− interpenetration in porphyrinic MOFs structure have not been realized to enhance their OL effect. Furthermore, since the incorporation of nanomaterials into flexible and transparent matrixes can effectively avoid aggregation, improve the stability, and reduce optical scattering, the exploration of new flexible and transparent MOFs-based composite materials with excellent OL is crucial for practical nonlinear optical applications.…”

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework Films for Giant Nonlinear Optical Limiting

“…28,29 As a branch of MOFs, porphyrinic MOFs 30 are attracting great attention on the third-order NLO performance because of their highly delocalized π-electronic conjugated system. 31,32 Generally, 3D porous porphyrinic MOFs with a weak π−π interaction have greatly limited performance, and they usually need to be loaded with guest species in their pores to enhance the third-order NLO performance. 33,34 Instead, 2D porphyrinic MOFs possess a huge number of π−π interactions between layers.…”

“…Third-order nonlinear optical (NLO) materials have recently received significant attention owing to their potential civilian and military applications in optical limiting (OL), mode-locked laser systems and optical switching, etc. − Many efforts made in third-order NLO materials mainly include organic molecules, inorganic semiconductors, carbon materials, and inorganic–organic hybrid materials, etc. − As a kind of ordered crystalline network material, metal–organic frameworks (MOFs) − assembled by metal nodes (or clusters) and organic linkers via coordination bonding have been widely reported in various optical fields including NLO behavior, − photodetectors, photocatalysis, − and so on. , As a branch of MOFs, porphyrinic MOFs are attracting great attention on the third-order NLO performance because of their highly delocalized π-electronic conjugated system. , Generally, 3D porous porphyrinic MOFs with a weak π–π interaction have greatly limited performance, and they usually need to be loaded with guest species in their pores to enhance the third-order NLO performance. , Instead, 2D porphyrinic MOFs possess a huge number of π–π interactions between layers. Great efforts in exploring the NLO properties of MOFs have been made, but third-order NLO in 2D MOFs with abundant π–π stacking have rarely been studied.…”

Recent advances of multiphoton absorption in metal–organic frameworks

“…Furthermore, in 2020 Young and co-workers published four porphyrin based coordination polymers built from H 2 TMPP (meso-tetrakis(6-methylpyridin-3-yl)porphyrin) and H 2 THPP (meso-tetra(6-(hydroxymethyl)pyridin3-yl)porphyrin) linker molecules and zinc and manganese as metal-precursor. 150 The optical properties of the synthesized materials were investigated using Z-scan technique, showing third-order hyperpolarizabilities in the range of 1.42 × 10 −28 esu to 7.64 × 10 −28 esu. These properties demonstrate themselves comparable to the best porphyrin-based MOF materials, which makes them suitable for optical limiting applications.…”