Synthesis and Third‐Order Nonlinear Optical Properties of a Conjugated Porphyrin Polymer

Abstract

Materials with large third-order optical nonlinearity are potentially useful for the fabrication of fast optical switches, but very few materials have sufficiently high susceptibility, ,yi3'. There is particular demand for materials with high ,y'3' ( > esu) in the near IR region (ca. 1 pm wavelength) for telecommunication switches. The molecular design features for a high xt3) material are poorly understood, although long conjugation lengths and low HOMO-LUMO gaps both appear to be important. ['] Porphyrins are appealing units from which to build high xi3' materials because of their large polarizable n systems. Here we report the synthesis of a conjugated porphyrin polymer (l), which exhibits an unusually high susceptibility x '~' , as revealed by its electroabsorption (Stark effect) spectrum, which is much more intense than those of model compounds such as the dimer 2 and the monomer 3. r R? i Polymer 1Compound 1 is the first soluble conjugated porphyrin polymer. Edge-fused conjugated porphyrin oligomers, and an insoluble polymer, have previously been synthesized.[21 Coordination polymers have also been investigatedC31 in which the metalloporphyrins are linked face-to-face; these exhibit much less intermacrocycle electronic coupling than polymer 1, in which the TC systems are edge-to-edge. Compound 1 was synthesized by

Meso-Linked Multiporphyrins as Model for Light Harvesting Systems: Review

“…In the covalently linked porphyrin arrays, a variety of linkages such as ethyne [36,37], polyyne [38][39][40], ethylene [41], alkane [42,43] and aromatic entities [44][45][46] have been used to bridge the individual porphyrins. Lindsey et al have reported the synthesis of numerous phenylene-and diphenyl ethynyl-bridged multiporphyrins for mimicking the biological light-harvesting antenna systems and their photo physical properties have been studied [46][47][48].…”

“…However, these porphyrin arrays show very weak ground-state electronic interactions between the porphyrin units. Various linear types of meso-to meso acetyleneand butadiyne-bridged multiporphyrins have also been reported and their photo physical and electrochemical properties have been determined [36][37][38]. In contrast to the arene-bridged porphyrin arrays, these types of multiporphyrins exhibit strong ground-and excitedstate interporphyrin electronic coupling.…”

Metalloporphyrins—Applications and clinical significance

“…Porphyrins have been incorporated into polymers as pendant groups, in the backbone of networks (36) and linear polymers and as coordination polymers. Thin films for catalysis studies have been prepared on electrodes by electropolymerization (37,38). Free-floating films, synthesized by interfacial condensation, can be supported on polymer membranes.…”

XPS Studies of Asymmetrical Tetraarylporphyrins and Their Ytterbium Complexes

“…[1][2][3][4] Наряду с этим, порфирины широко используются в медицине благодаря своей способности селективно накапливаться в злокачественных новообразованиях. Это уникальное свойство порфиринов лежит в основе фотодинамической терапии рака, а также для прове-дении флуоресцентной диагностики.…”