A computational approach for calculating the distortions in the lowest energy triplet metal to ligand charge-transfer ((3)MLCT = T(0)) excited states of ruthenium(II)-bipyridine (Ru-bpy) complexes is used to account for the patterns of large variations in vibronic sideband amplitudes found in the experimental 77 K emission spectra of complexes with different ancillary ligands (L). Monobipyridine, [Ru(L)(4)bpy](m+) complexes are targeted to simplify analysis. The range of known emission energies for this class of complexes is expanded with the 77 K spectra of the complexes with (L)(4) = bis-acetonylacetonate (emission onset at about 12,000 cm(-1)) and 1,4,8,11-tetrathiacyclotetradecane and tetrakis-acetonitrile (emission onsets at about 21,000 cm(-1)); no vibronic sidebands are resolved for the first of these, but they dominate the spectra of the last two. The computational modeling of excited-state distortions within a Franck-Condon approximation indicates that there are more than a dozen important distortion modes including metal-ligand modes (low frequency; lf) as well as predominately bpy modes (medium frequency; mf), and it simulates the observed 77 K emission spectral band shapes of selected complexes very well. This modeling shows that the relative importance of the mf modes increases very strongly as the T(0) energy increases. Furthermore, the calculated metal-centered SOMOs show a substantial bpy-π-orbital contribution for the complexes with the highest energy T(0). These features are attributed to configurational mixing between the diabatic MLCT and the bpy (3)ππ* excited states at the highest T(0) energies.
The lowest energy metal to ligand charge transfer (MLCT) absorption bands found in ambient solutions of [Ru(NH(3))(4)(Y-py)(2)](2+) and [Ru(L)(2)(bpy)(2)](+) complexes (Y-py a pyridine ligand and (L)(n) a substituted acetonylacetonate, halide, am(m)ine, etc.) consist of two partly resolved absorption envelopes, MLCT(lo) and MLCT(hi). The lower energy absorption envelope, MLCT(lo), in these spectra has the larger amplitude for the bis-(Y-py) complexes, but the smaller amplitude for the bis-bpy the complexes. Time-dependent density functional theory (TD-DFT) approaches have been used to model 14 bis-bpy, three bis-(Y-py), and three mono-bpy complexes. The modeling indicates that the lowest unoccupied molecular orbital (LUMO) of each bis-(Y-py) complex corresponds to the antisymmetric combination of individual Y-py acceptor orbitals and that the transition involving the highest occupied molecular orbital (HOMO) and LUMO (HOMO-->LUMO) is the dominant contribution to MLCT(lo) in this class of complexes. The LUMO of each bis-bpy complex that contains a C(2) symmetry axis also corresponds largely to the antisymmetric combination of individual ligand acceptor orbitals, while the LUMOs are more complex when there is no C(2) axis; furthermore, the energy difference between the HOMO-->LUMO and HOMO-->LUMO+1 transitions is too small (<1000 cm(-1)) to resolve in the spectra of the bis-bpy complexes in ambient solutions. Relatively weak MLCT(lo) absorption contributions are found for all of the [Ru(L)(2)(bpy)(2)](m+) complexes examined, but they are experimentally best defined in the spectra of the (L)(2) = X-acac complexes. TD-DFT modeling of the HOMO-->LUMO transition of [Ru(L)(4)bpy](m+) complexes indicates that it is too weak to be detected and occurs at significantly lower energy (about 3000-5000 cm(-1)) than the observed MLCT absorptions. Since the chemical properties of MLCT excited states are generally correlated with the HOMO and/or LUMO properties of the complexes, such very weak HOMO-->LUMO transitions can complicate the use of spectroscopic information in their assessment. As an example, it is observed that the correlation lines between the absorption energy maxima and the differences in ground state oxidation and reduction potentials (DeltaE(1/2)) have much smaller slopes for the bis-bpy than the mono-bpy complexes. However, the observed MLCT(lo) and the calculated HOMO-->LUMO transitions of bis-bpy complexes correlate very similarly with DeltaE(1/2) and this indicates that it is the low energy and small amplitude component of the lowest energy MLCT absorption band that is most appropriately correlated with excited state chemistry, not the absorption maximum as is often assumed.
In this study, we compare the proteasome inhibition capabilities of two anticancer candidates, [Ni(LIA)2] (1) and [Zn(LIA)2] (2), where LIA- is the deprotonated form of the ligand 2,4-diiodo-6-(((2-pyridinylmethyl)amino)methyl)phenol. Species 1 contains nickel(II), a considerably inert ion that favors covalency, whereas 2 contains zinc(II), a labile transition metal ion that favors predominantly ionic bonds. We report on the synthesis and characterization of 1 and 2 using various spectroscopic, spectrometric, and structural methods. Furthermore, the pharmacological effects of 1 and 2, along with the salts NiCl2 and ZnCl2, were evaluated in vitro and in cultured human cancer cells in terms of their proteasome-inhibitory and apoptotic cell death-inducing capabilities. It is shown that neither NiCl2 nor 1 have the ability to inhibit the proteasome activity at any sustained levels. However, ZnCl2 and 2 showed superior inhibitory activity to the chymotrypsin-like activity of both 26S proteasome (IC50 = 5.7 and 4.4 μmol/L, respectively) and purified 20S proteasome (IC50 = 16.6 and 11.7 μmol/L, respectively) under cell-free conditions. Additionally, inhibition of proteasomal activity in cultured prostate cancer cells by 2 was associated with higher levels of ubiquitinated proteins and apoptosis. Treatment with either the metal complex or the salt was relatively non-toxic toward human normal cells. These results strengthen the current working hypothesis that fast ligand dissociation is required to generate an [MLIA]+ pharmacophore, capable of interaction with the proteasome. This interaction, possibly via N-terminal threonine aminoacids present in the active sites, renders the proteasome inactive. Our results present a compelling rationale for 2, along with its gallium(III) and copper(II) congeners to be further investigated as potential anticancer drugs that act as proteasome inhibitiors.
In order to understand and predict structural, redox, magnetic, and optical properties of more complex and potentially mesogenic electroactive compounds such as [Co(III)(L(t-BuLC))2]ClO4 (1), five archetypical complexes of general formula [Co(III)(L(RA))2]ClO4, where R = H (2), tert-butyl (3), methoxy (4), nitro (5), and chloro (6), were obtained and studied by means of several spectrometric, spectroscopic, and electrochemical methods. The complexes 2, 4, and 6 were characterized by single-crystal X-ray diffraction, and show the metal center in an approximate D2h symmetry. Experimental results support the fact that the electron donating or withdrawing nature of the phenolate-appended substituents changes dramatically the redox and spectroscopic properties of these compounds. The 3d6 electronic configuration of the metal ion dominates the overall geometry adopted by these compounds with the phenolate rings occupying trans positions to one another. Formation of phenoxyl radicals has been observed for 1, 3, and 6, but irreversible ligand oxidation takes place upon bulk electrolysis. These data were compared to detailed B3LYP/6-31G (d)-level computational calculations and have been used to account for the results observed. A comparison between compound 1 and archetype 3, validates the approach of using archetypical models to study metal-containing soft materials.
The lowest energy metal-to-ligand charge transfer (MLCT) absorption bands found in ambient solutions of a series of [Ru(tpy)(bpy)X](m+) complexes (tpy = 2,2':3',2''-terpyridine; bpy = 2,2'-bipyridine; and X = a monodentate ancillary ligand) feature one or two partly resolved weak absorptions (bands I and/or II) on the low energy side of their absorption envelopes. Similar features are found for the related cyanide-bridged bi- and trimetallic complexes. However, the weak absorption band I of [(bpy)(2)Ru{CNRu(tpy)(bpy)}(2)](4+) is missing in its [(bpy)(2)Ru{NCRu(tpy)(bpy)}(2)](4+) linkage isomer demonstrating that this feature arises from a Ru(II)/tpy MLCT absorption. The energies of the MLCT band I components of the [Ru(tpy)(bpy)X](m+) complexes are proportional to the differences between the potentials for the first oxidation and the first reduction waves of the complexes. Time-dependent density functional theory (TD-DFT) computational modeling indicates that these band I components correspond to the highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition, with the HOMO being largely ruthenium-centered and the LUMO largely tpy-centered. The most intense contribution to a lowest energy MLCT absorption envelope (band III) of these complexes corresponds to the convolution of several orbitally different components, and its absorption maximum has an energy that is about 5000 cm(-1) higher than that of band I. The multimetallic complexes that contain Ru(II) centers linked by cyanide have mixed valence excited states in which more than 10% of electronic density is delocalized between the nearest neighbor ruthenium centers, and the corresponding stabilization energy contributions in the excited states are indistinguishable from those of the corresponding ground states. Single crystal X-ray structures and computational modeling indicate that the Ru-(C≡N)-Ru linkage is quite flexible and that there is not an appreciable variation in electronic structure or energy among the conformational isomers.
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