Coordination nonlinear optical activities

Orientation of nonlinear optical active dyes in electrostatically self-assembled polymer films containing cyclodex-trins was studied. "The concept of molecular recognition of organic chromophores by coordinating polymers was another novel approach in the construction of nonlinear optical supramolecular assemblies. 

Han L, Hong M, Wang R, Luo J, Lin Z, Yuan D (2003) A novel nonlinear optically active tubular coordination network based on two distinct homo-chiral helices. Chem Commun 2580-2581... 

The coordination chemistry of the trichalcogenophosphonates is very undeveloped when compared to the analogous metal organophosphonates (RP032), which have been extensively studied owing to their potential and practical applications as ion exchangers, sorbents, sensors, proton conductors, nonlinear optical materials, photochemically active materials, catalysts and hosts for the intercalation of a broad spectrum of guests.145... 

Oligomerization and polymerization of terminal alkynes may provide materials with interesting conductivity and (nonlinear) optical properties. Phenylacetylene and 4-ethynyltoluene were polymerized in water/methanol homogeneous solutions and in water/chloroform biphasic systems using [RhCl(CO)(TPPTS)2] and [IrCl(CO)(TPPTS)2] as catalysts [37], The complexes themselves were rather inefficient, however, the catalytic activity could be substantially increased by addition of MesNO in order to remove the carbonyl ligand from the coordination sphere of the metals. The polymers obtained had an average molecular mass of = 3150-16300. The rhodium catalyst worked at room temperature providing polymers with cis-transoid structure, while [IrCl(CO)(TPPTS)2] required 80 °C and led to the formation of frani -polymers. 

In impulsive multidimensional (1VD) Raman spectroscopy a sample is excited by a train of N pairs of optical pulses, which prepare a wavepacket of quantum states. This wavepacket is probed by the scattering of the probe pulse. The electronically off-resonant pulses interact with the electronic polarizability, which depends parametrically on the vibrational coordinates (19), and the signal is related to the 2N + I order nonlinear response (18). Seventh-order three-dimensional (3D) coherent Raman scattering, technique has been proposed by Loring and Mukamel (20) and reported in Refs. 12 and 21. Fifth-order two-dimensional (2D) Raman spectroscopy, proposed later by Tanimura and Mukamel (22), had triggered extensive experimental (23-28) and theoretical (13,25,29-38) activity. Raman techniques have been reviewed recently (12,13) and will not be discussed here. 

Lattice inclusion of organic chromophores inside coordination polymers has also been used to achieve optical nonlinear effects. A SHG-active compound [ Cd(4,4 -bpy)2(H20)2 4,4 -bpy2 (2-nitroaniline) 2C104 H20] , cocrystallized in the monoclinic space group Cc, has 2-D square grids (Scheme 4a) with 2-nitroaniline molecules, which is a NLO-active organic chromophore. ... 

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