Ruthenium Complexes Containing 2, 2′‐Bipyridine and 1, 3, 5‐Triaza‐7‐phosphaadamantane. Issue 10 (4th March 2016)

• Record Type: Journal Article
• Authors: Scalambra, Franco; Serrano‐Ruiz, Manuel; Nahim‐Granados, Samira; Romerosa, Antonio
• Is Part Of: European journal of inorganic chemistry. Issue 10(2016)
• Page Start: 1528
• Page End: 1540
• Publication Date: 2016-03-04
• Subjects: Ruthenium -- N, P ligands -- Fluorescence -- Redox chemistry -- Photochemistry -- Water‐soluble complexes; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501357
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Water‐soluble complexes cis ‐[Ru(bpy)2 (PTA)2 ]Cl2 (1 Cl2 ), cis ‐[Ru(bpy)2 (PTA)2 ](PF6 )2 [1 (PF6 )2 ], trans ‐[Ru(bpy)2 (PTA)2 ](CF3 SO3 )2 [2 (CF3 SO3 )2 ], cis ‐[Ru(bpy)2 (PTA)(H2 O)](CF3 SO3 )2 [3 (CF3 SO3 )2 ], cis ‐[Ru(bpy)2 (PTAH)(H2 O)](CF3 SO3 )3 · 2CF3 SO3 H [4 (CF3 SO3 )3 · 2CF3 SO3 H], cis ‐[Ru(bpy)2 (PTAH)2 ](CF3 SO3 )4 · 4CF3 SO3 H [5 (CF3 SO3 )4 · 4CF3 SO3 H], and trans ‐[Ru(bpy)2 (PTAH)2 ](CF3 SO3 )4 · 4CF3 SO3 H [6 (CF3 SO3 )4 · 4CF3 SO3 H] (bpy = 2, 2′‐bipyridyl; PTA = 1, 3, 5‐triaza‐7‐phosphaadamantane) have been synthesized and characterized by elemental analysis, NMR, and IR spectroscopy. The crystal structures of1 (PF6 )2, 2 (CF3 SO3 )2, and3 (CF3 SO3 )2 were obtained by single‐crystal X‐ray diffraction. Both experimental and computational techniques were utilized to perform a detailed analysis of the structural and electronic properties of complexes1 and2 in water in both the deprotonated and protonated state and under N2 and air. Luminescence studies showed that these complexes are active fluorescence compounds, despite the presence of monophosphines in their structure. The pH sensitivity of the emission band of both complexes and their photohydrolysis in acidic water solution was studied. Both complexes release a PTA molecule under selective irradiation in acidic water to give complex4 . Cyclic voltammetry showed that, in water, irreversible anodic oxidation corresponding to the Ru II /Ru III redox process occurs for1, whereas for2 the process is quasi‐reversible, while in N, N ‐dimethylformamide for both complexes they are irreversible and occur at lower potential than in water. Abstract : New water‐soluble ruthenium complexes containing 1, 3, 5‐triaza‐7‐phosphaadamantane (PTA) and 2, 2′‐bipyridine were characterized, and their optical properties in water were studied. Luminescence studies on these pH‐sensitive complexes showed that they are active fluorescence compounds, despite the presence of monophosphines in their structure.