Syntheses, Crystal Structures, and Optical Properties of Metal Complexes with 4′,5′-Diaza-9′-(4,5-disubstituted-1,3-dithiol-2-ylidene)fluorene Ligands

• Published in: European Journal of Inorganic Chemistry 2008-01, Vol.2008 (2), p.230-238
• Main Authors: Zhu, Qin-Yu, Lu, Wen, Zhang, Yong, Bian, Guo-Qing, Gu, Jing, Lin, Xiao-Min, Dai, Jie
• Format: Article
• Language: English
• Subjects: Crystal structure; Dithioles; Fluorenes; Metal complexes; Optical properties
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200700862

Four complexes with 4′,5′‐diaza‐9′‐[4,5‐bis(methylthio)‐1,3‐dithiol‐2‐ylidene]fluorene (L1) or 4′,5′‐diaza‐9′‐[4,5‐bis(ethylthio)‐1,3‐dithiol‐2‐ylidene]fluorene (L2) were synthesized. The complexes [Co(L1)2Cl2]·2CH3OH (1), [Cu(L2)2Cl2]·CH3OH·0.5CH2Cl2 (3), and [Cu(L2)2Br2]·CH3OH (4) adopt a trans configuration and the compound [Cd(L1)2(NO3)2] (2) is a cis structure. Short S···S, C···C, and C···S contacts were found to be important in the molecular packing. Both the solution and solid‐state electronic spectra show a redshift in the intramolecular CT bands when forming metal complexes. This intramolecular charge transition in the solid state is enhanced relative to that in solution. Their third‐order nonlinear optical properties of compounds 1–4 were studied, and the results reveal that these complexes exhibit negative γ values (about 10–30) and are self‐defocusing samples. These γ values are comparable to those of the known cluster compounds. The trans coordination of the two ligands to the metal center would be beneficial to the NLO properties. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)