Reversible Photoswitching of Second-Order Nonlinear Optical Properties in an Organic Photochromic Crystal

Efficient, Reversible Redox-Switching of Molecular First Hyperpolarizabilities in Ruthenium(II) Complexes Possessing Large Quadratic Optical Nonlinearities

“…[13c] Metathesis to the chloride salts is exemplified as follows: [1](PF 6 ) 3 (88 mg, 0.11 mmol) was dissolved in acetone (5 mL) and a solution of [N(nBu) 4 ]Cl (0.5 g, 1.80 mmol) in acetone (5 mL) was added dropwise. The deep blue precipitate was filtered off, washed thoroughly with acetone, and dried under vacuum (CaSO 4 ) at ambient temperature to afford [1] The experimental details of the HRS measurements have been described previously.…”

“…[2] In spite of these interesting featuresÐand in addition possible variation of conformational organization, substitution of the upper and lower rims, and shape and sizeÐonly limited efforts have been made to construct biologically relevant calixarenes containing carbohydrate moieties. [3,4] In line with this concept, the synthesis of nondendritic galactose octamers attached to a calix [4]resorcarene scaffold possessing lipophilic side chains has been described. However, as opposed to our work presented herein, the hydrophilic carbohydrate residues were used for polar attachment to a polar quartz surface.…”

“…However, as opposed to our work presented herein, the hydrophilic carbohydrate residues were used for polar attachment to a polar quartz surface. [5] We describe here the first synthesis of dendritic, [6] watersoluble, carbohydrate-containing p-tert-butylcalix [4]arenes and their lectin-binding properties. These carbohydrate-containing calix [4]arenes can serve as models to further investigate factors influencing multivalent carbohydrate ± protein interactions at the molecular level.…”

“…[5] We describe here the first synthesis of dendritic, [6] watersoluble, carbohydrate-containing p-tert-butylcalix [4]arenes and their lectin-binding properties. These carbohydrate-containing calix [4]arenes can serve as models to further investigate factors influencing multivalent carbohydrate ± protein interactions at the molecular level. The lipophilic p-tert-butyl substituents provide the driving force for stable assembly and/ or adhesion of a calixarene monolayer to a surface, while the hydrophilic carbohydrate ligands mimic the cells sacchariderich surface.…”

“…Photoswitching of SHG has been observed recently in solutions of bacteriorhodopsin [3] and in crystals of N-salicylidene-4-bromoaniline. [4] In other studies focusing on molecular properties, a bis(thienyl)ethene was found to exhibit a change in b on photoisomerization, [5] and it has been suggested that photoinduced proton-transfer may alter b in nitrobenzyl pyridines. [7] Transition metal organometallic and coordination complexes are an important class of NLO molecules, [1d, 8] for which b data is becoming increasingly available, [8,9] largely due to the introduction of the versatile hyper-Rayleigh scattering (HRS) technique.…”