Optically Tunable Nonlinearities in Polymers Based on Photoisomerizable Metal-Based Coordination Complexes

Multiphotochromic molecular systems

“…This increase is logically reached at the price of a decrease in the proportion of the EZ intermediate obtainable. Similar AZB dimers corresponding to the substitution of a bipyridine unit at the 4,4 0 positions have also been obtained by Le Bozec and coworkers, [126][127][128] though they were primarily designed to be used as ligands in a coordination complex, and are thus discussed in Section 4.…”

“…Zn(II) complexes 112 and 113 possess respectively one and three 2,2-bipyridine ligands substituted at the 4,4-positions by two AZB units. [126][127][128] With the aim to obtain NLO switchable materials, these compounds have been designed to be implemented in a PMMA matrix through an atom transfer radical polymerization (ATRP) of their terminal alkyl chains. In solution, 113 complex exhibited an isomerisation qualitatively similar to the metal-free AZB dyad ligand, though this isomerisation is quantitatively less efficient: the total photoconversion reaches 53% for the ligand but 25% for 113.…”

Soluble dynamic coordination polymers as a paradigm for materials science

“…These polymers are now intensely studied due to their unusual properties provided by the metal ion, e.g. molecular-magnetism [8][9][10][11][12][13], synthetic metallic conduction [14][15][16][17], non-linear optics [18][19][20][21] and ferroelectrics [22][23][24][25], and this, in combination with the outstanding mechanical properties of conventional polymers. The possibility to modify their magnetic, electric and optical properties as well as their morphology by the choice of the involved metal ions and the manipulation of its redox properties in addition to the ligands opens pathways to a completely new class of functional materials.…”

Zinc(II) as a Versatile Template for Efficient Dipolar and Octupolar Second-Order Nonlinear Optical Molecular Materials §

“…In order to achieve the macroscopic noncentrosymmetric orientation of these octupolar chromophores, the so-called "all-optical poling" technique [74], which is an interference process between one and two-photon excitations that locally induces macroscopic second-order effects in polymer films, has been employed. To this end, octupolar tris(bipyridyl)Zn(II) complexes containing three photoisomerizable ligands, such as 4,4′-bis-(styryl)-2,2′-bipyridine functionalized with a dialkylamino-azobenzene, 33, were synthesized and studied [75,76]. These complexes allowed the synthesis of star-shaped polymers, in which the octupolar molecules are covalently linked to the organic backbone, 34.…”

“…polymer films, has been employed. To this end, octupolar tris(bipyridyl)Zn(II) complexes containing three photoisomerizable ligands, such as 4,4′-bis-(styryl)-2,2′-bipyridine functionalized with a dialkylamino-azobenzene, 33, were synthesized and studied [75,76]. These complexes allowed the synthesis of star-shaped polymers, in which the octupolar molecules are covalently linked to the organic backbone, 34.…”