Organometallic Complexes for Nonlinear Optics. 8.1Syntheses and Molecular Quadratic Hyperpolarizabilities of Systematically Varied (Triphenylphosphine)gold σ-Arylacetylides: X-ray Crystal Structures of Au(C⋮CR)(PPh3) (R = 4-C6H4NO2, 4,4‘-C6H4C6H4NO2)
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Abstract
The series of complexes Au(C⋮CR)(PPh3) (R = Ph (2), 4-C6H4NO2 (3), 4,4‘-C6H4C6H4NO2 (4), (E)-4,4‘-C6H4CHCHC6H4NO2 (5), (Z)-4,4‘-C6H4CHCHC6H4NO2 (6), 4,4‘-C6H4C⋮CC6H4NO2 (7), 4,4‘-C6H4NCHC6H4NO2 (8)) have been synthesized by reaction of AuCl(PPh3) with the corresponding acetylene and methoxide, and complexes 3−8 have been structurally characterized. The molecular first hyperpolarizabilities for the complexes have been determined by hyper-Rayleigh scattering at 1064 nm. Introduction of the nitro substituent (in proceeding from 2 to 3) leads to a significant increase in nonlinearity. Experimental β values increase as 3 < 4 < 6 ≈ 7 < 8 < 5 consistent with nonlinearity increasing with (i) chain lengthening, (ii) replacing biphenyl (4) or yne linkage (7) by ene linkage (5), (iii) replacing (Z)-ene stereochemistry (6) with (E)-ene stereochemistry (5), and (iv) ene linkage (5) being more efficient than imino linkage (8). The same trend is observed with two-level-corrected data. A linear correlation of both experimentally-determined and two-level-corrected nonlinearities of the acetylides with precursor acetylenes is observed.
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