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Ruthenium Complexes Containing 2,2′‐Bipyridine and 1,3,5‐Triaza‐7‐phosphaadamantane
Author(s) -
Scalambra Franco,
SerranoRuiz Manuel,
NahimGranados Samira,
Romerosa Antonio
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501357
Subject(s) - chemistry , ruthenium , protonation , deprotonation , luminescence , nuclear magnetic resonance spectroscopy , crystal structure , medicinal chemistry , crystallography , bipyridine , stereochemistry , catalysis , organic chemistry , ion , physics , optoelectronics
Water‐soluble complexes cis ‐[Ru(bpy) 2 (PTA) 2 ]Cl 2 ( 1 Cl 2 ), cis ‐[Ru(bpy) 2 (PTA) 2 ](PF 6 ) 2 [ 1 (PF 6 ) 2 ], trans ‐[Ru(bpy) 2 (PTA) 2 ](CF 3 SO 3 ) 2 [ 2 (CF 3 SO 3 ) 2 ], cis ‐[Ru(bpy) 2 (PTA)(H 2 O)](CF 3 SO 3 ) 2 [ 3 (CF 3 SO 3 ) 2 ], cis ‐[Ru(bpy) 2 (PTAH)(H 2 O)](CF 3 SO 3 ) 3 · 2CF 3 SO 3 H [ 4 (CF 3 SO 3 ) 3 · 2CF 3 SO 3 H], cis ‐[Ru(bpy) 2 (PTAH) 2 ](CF 3 SO 3 ) 4 · 4CF 3 SO 3 H [ 5 (CF 3 SO 3 ) 4 · 4CF 3 SO 3 H], and trans ‐[Ru(bpy) 2 (PTAH) 2 ](CF 3 SO 3 ) 4 · 4CF 3 SO 3 H [ 6 (CF 3 SO 3 ) 4 · 4CF 3 SO 3 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 of 1 (PF 6 ) 2 , 2 (CF 3 SO 3 ) 2 , and 3 (CF 3 SO 3 ) 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 complexes 1 and 2 in water in both the deprotonated and protonated state and under N 2 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 complex 4 . Cyclic voltammetry showed that, in water, irreversible anodic oxidation corresponding to the Ru II /Ru III redox process occurs for 1 , whereas for 2 the process is quasi‐reversible, while in N , N ‐dimethylformamide for both complexes they are irreversible and occur at lower potential than in water.