Tetrathiafulvalene-Triazine-Dipyridylamines as Multifunctional Ligands for Electroactive Complexes: Synthesis, Structures, and Theoretical Study

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• 作者：Diana G. Branzea ; Arnaud Fihey ; Thomas Cauchy ; Abdelkrim El-Ghayoury ; Narcis Avarvari
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：August 6, 2012
• 年：2012
• 卷：51
• 期：15
• 页码：8545-8556
• 全文大小：813K
• 年卷期：v.51,no.15(August 6, 2012)
• ISSN：1520-510X

文摘

The electroactive ligands (2,4-bis-tetrathiafulvalene[6-(dipyridin-2鈥?ylamino)]-1,3,5-triazine) TTF₂-tz-dpa (1) and (2-tetrathiafulvalene[4,6-bis-(dipyridin-2鈥?ylamino)]-1,3,5-triazine) TTF-tz-dpa₂ (2) have been synthesized by palladium cross-coupling catalysis, and the single crystal X-ray structure for 1 was determined. In the solid state the TTF and triazine units are practically coplanar and short intermolecular S路路路S contacts are established. Two neutral and one tetracationic Zn(II) complexes, formulated as (TTF₂-tz-dpa)ZnCl₂ (3), [ZnCl₂(TTF-tz-dpa₂)Zn(H₂O)Cl₂] (4), and {[(H₂O)₂Zn(TTF-tz-dpa₂)](ClO₄)₂}₂ (5) have been crystallized and analyzed by single crystal X-ray analysis. A peculiar feature is the evidence for anion-蟺 interactions, as shown by the short Cl路路路triazine and O(perchlorate)路路路triazine distances of 3.52 and 3.00 脜, respectively. A complex set of intermolecular 蟺路路路蟺, S路路路S, and hydrogen bonding interactions sustain the supramolecular organizations of the complexes in the solid state. Electronic absorption spectra provide evidence for the intramolecular charge transfer from TTF to triazine, also supported by time-dependent density functional theory (TD DFT) calculations.