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Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties
Author(s) -
Recatalá David,
Llusar Rosa,
Galindo Francisco,
Brylev Konstantin A.,
Gushchin Artem L.
Publication year - 2015
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.201403228
Subject(s) - chemistry , diimine , phenanthroline , luminescence , dichloromethane , molybdenum , quantum yield , valence (chemistry) , crystallography , halide , excited state , ligand (biochemistry) , ion , cluster (spacecraft) , fluorescence , medicinal chemistry , inorganic chemistry , solvent , catalysis , organic chemistry , nuclear physics , programming language , biochemistry , physics , receptor , optoelectronics , quantum mechanics , computer science
Neutral Mo 3 (μ 3 ‐S)(μ‐S 2 ) 3 X 3 (diimine) (X = Cl – , Br – ) heteroleptic cluster complexes containing the 1,10‐phenanthroline ligands 1 H ‐imidazo[4,5‐ f ][1,10]phenanthroline‐2‐[3,4‐bis(dodecyloxy)phenyl] (IPDOP), 4,7‐diphenyl‐1,10‐phenanthroline (BPhen), and 3,4,7,8‐tetramethyl‐1,10‐phenanthroline (tmphen) were prepared in high yields by straightforward ligand‐substitution reactions starting from the [Mo 3 (μ 3 ‐S)(μ‐S 2 ) 3 X 6 ] 2– cluster anion. The complexes Mo 3 S 7 X 4 (BPhen) [X = Br – (for 3 ) and Cl – (for 4 )] and Mo 3 S 7 X 4 (tmpphen) [X = Br – (for 5 ) and Cl – (for 6 )] crystallized as tetra‐ n ‐butylammonium salts of anionic aggregates ( 3 – 6· X) – , in which neutral Mo 3 S 7 X 3 (diiimine) 3 cluster molecules participate in non‐valence interactions between the axial sulfur atoms, S ax , and a halide anion. The complexes Mo 3 S 7 Br 4 (IPDOP) ( 1 ) and Mo 3 S 7 Cl 4 (IPDOP) ( 2 ) are luminescent when excited at 330 nm and have maximum emission intensities around 450 nm in DMF and around 435 nm in dichloromethane. The maximum fluorescence quantum yield and the maximum emission lifetime were achieved for complex 2 in DMF( φ F = 0.15 and τ = 7.5 ns, respectively). The most important property of complexes 1 and 2 is the shift of their emission spectra in the presence of proton‐abstractor anions, such as F – , OH – , and AcO – . When these anions are added to solutions of complexes 1 or 2 in DMF or dichloromethane, the maximum emission wavelength shifts by approximately 90 nm to higher wavelengths.