H-bonded adducts of [2,4,6-{(C10H21O)3C6H2NH}3C3N3] with [LnM{PPh2(C6H4CO2

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• 作者：Ana B. Miguel-Coello ; Manuel Bardaj铆 ; Silverio Coco ; Bertrand Donnio ; Beno卯t Heinrich ; Pablo Espinet
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：October 20, 2014
• 年：2014
• 卷：53
• 期：20
• 页码：10893-10902
• 全文大小：580K
• ISSN：1520-510X

文摘

Displacement of a labile ligand from appropriate precursor complexes by 2- or 4-PPh₂C₆H₄COOH yields neutral gold(I) and gold(III) [AuX_n(PPh₂C₆H₄COOH)] (n = 1, X = Cl; n = 3, X = C₆F₅), cationic gold(I) [Au(PPh₂C₆H₄COOH)₂](CF₃SO₃), and neutral chromium(0) [Cr(CO)₅(PPh₂C₆H₄COOH)] metallo鈥搊rganic acids. [AuCl(4-PPh₂C₆H₄COOH)], [Au(C₆F₅)₃(4-PPh₂C₆H₄COOH)], and [Cr(CO)₅(2-PPh₂C₆H₄COOH)] have dimeric structures with typical carboxylic H-bond bridges, whereas [Au(C₆F₅)₃(2-PPh₂C₆H₄COOH)] gives a monomeric species with the carboxylic acid H bonded to cocrystallized solvent molecules. All gold-containing acids are emissive at 77 K in the range 404鈥?20 nm and some of them also at 298 K with emission maxima from 441 to 485 nm. Reaction of these acid metal complexes with the triazine mesogen 2,4,6-{(C₁₀H₂₁O)₃C₆H₂NH}₃C₃N₃ affords some new hydrogen-bonded gold(I) and chromium(0) supramolecular adducts, but the related gold(III) complexes do not form adducts. The 4-diphenylphosphinobenzoic adducts display a columnar hexagonal mesophase (Col_hex) at room temperature, with a random one-dimensional stacking of the pseudo-discoid triazine鈥搈etallo鈥搊rganic adducts into columns, where the metallo鈥損hosphinoacid fragments act as the fourth branch of the trifold triazine core. The 2-diphenylphosphinobenzoic mixtures do not display mesophases, as they appear in the X-ray studies as mixtures of the triazine and the metallo鈥損hosphinoacid complex. The aggregates are luminescent at 77 K, with emission maxima in the range 419鈥?55 nm.