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Trans Influence and Substituent Effects on the HOMO-LUMO Energy Gap and Stokes Shift in Ru Mono-Diimine Derivatives.

ABSTRACT: The ground (S0) and excited triplet (T1) electronic states and corresponding optical spectra of a series of cationic complexes [RuH(CO)L(PPh3)2]+ (L=2,2´-bipyridyl) (Rubpy), 4,4´-dicarboxylic-2,2´-bipyridyl (Rudcbpy), bis-4,4'-(N-methylamide)-2,2´-bipyridyl (Rudamidebpy), bis-4,4'-(methyl)-2,2´-bipyridyl (RudMebpy), [Ru(CO)2dcbpy(PPh3)2]2+ (Ru(2CO)dcbpy), and [Ru(H)2dcbpy(PPh3)2] (Ru(2H)dcbpy) have been studied by combined Density Functional/Time-Dependent Density Functional (DFT/TDDFT) techniques using different combinations of DFT exchange-correlation functionals and basis sets. PBE0/LANL2DZ provided more accurate geometries to describe S0 whereas B3LYP/LANL2DZ predicted spectral energies that correlated better with the available experiment data. The Ru (II) complexes with different substituents emit photons ranging from 560-610 nm in the series RudMebpy, Rubpy, Rudamidebpy, Rudcbpy. The calculations predicted a maximum emission at about 540 nm for the complex constructed from two carbonyl ?-acceptors ligands trans to the dcbpy, while an emission in the far infrared region is calculated when two H ?-donor ligands trans to the dcbpy. Our calculation results show correlations between HOMO-LUMO energy gap, Stokes shift, and T1 distortion, which reflect the different effects of electron-withdrawing and donating groups. We proposed that these correlations can be used to predict the photophysical properties for new complexes.

SUBMITTER: AlAbbad S

PROVIDER: S-EPMC7449144 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Trans Influence and Substituent Effects on the HOMO-LUMO Energy Gap and Stokes Shift in Ru Mono-Diimine Derivatives.

AlAbbad Sanaa S Sardot Tova T Lekashvili Oliko O Decato Daniel D Lelj Francesco F Alexander Ross J B JB Rosenberg Edward E

Journal of molecular structure 20190610

The ground (S0) and excited triplet (T1) electronic states and corresponding optical spectra of a series of cationic complexes [RuH(CO)L(PPh3)2]+ (L=2,2´-bipyridyl) (Rubpy), 4,4´-dicarboxylic-2,2´-bipyridyl (Rudcbpy), bis-4,4'-(N-methylamide)-2,2´-bipyridyl (Rudamidebpy), bis-4,4'-(methyl)-2,2´-bipyridyl (RudMebpy), [Ru(CO)2dcbpy(PPh3)2]2+ (Ru(2CO)dcbpy), and [Ru(H)2dcbpy(PPh3 ...[more]

PMID: 32863429

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Project description:The series of complexes [XRu(CO)(L-L)(L')2][PF6] (X = H, TFA, Cl; L-L = 2,2'-bipyridyl, 1,10-phenanthroline, 5-amino-1,10-phenanthroline and 4,4'-dicarboxylic-2,2'-bipyridyl; L'2 = 2PPh3, Ph2 PC2H4PPh2, Ph2PCH?CHPPh2) have been synthesized from the starting complex K[Ru(CO)3(TFA)3] (TFA = CF3CO2) by first reacting with the phosphine ligand, followed by reaction with the L-L and anion exchange with NaPF6. In the case of L-L = phenanthroline and L'2 = 2PPh3, the neutral complex Ru(Ph3P)(CO)(1,10-phenanthroline)( TFA)2 is also obtained and its solid state structure is reported. Solid state structures are also reported for the cationic complexes where L-L = phenanthroline, L2 = 2PPh3 and X = Cl and for L-L = 2,2'-bipyridyl, L2 = 2PPh3 and X = H. All the complexes were characterized in solution by a combination of 1H and 31P NMR, IR, mass spectrometry and elemental analyses. The purpose of the project was to synthesize a series of complexes that exhibit a range of excited-state lifetimes and that have large Stokes shifts, high quantum yields and high intrinsic polarizations associated with their metal-to-ligand charge-transfer (MLCT) emissions. To a large degree these goals have been realized in that excited-state lifetimes in the range of 100 ns to over 1 ?s are observed. The lifetimes are sensitive to both solvent and the presence of oxygen. The measured quantum yields and intrinsic anisotropies are higher than for previously reported Ru(II) complexes. Interestingly, the neutral complex with one phosphine ligand shows no MLCT emission. Under the conditions of synthesis some of the initially formed complexes with X = TFA are converted to the corresponding hydrides or in the presence of chlorinated solvents to the corresponding chlorides, testifying to the lability of the TFA Ligand. The compounds show multiple reduction potentials which are chemically and electrochemically reversible in a few cases as examined by cyclic voltammetry. The relationships between the observed photophysical properties of the complexes and the nature of the ligands on the Ru(II) is discussed.

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Trans Influence and Substituent Effects on the HOMO-LUMO Energy Gap and Stokes Shift in Ru Mono-Diimine Derivatives.

Publications

<i>Trans</i> Influence and Substituent Effects on the HOMO-LUMO Energy Gap and Stokes Shift in Ru Mono-Diimine Derivatives.

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