Dynamical and Environmental Effects on the Optical Properties of an Heteroleptic Ru(II)–Polypyridine Complex: A Multilevel Approach Combining Accurate Ground and Excited State QM-Derived Force Fields, MD and TD-DFT

Abstract

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Iron’s Wake: The Performance of Quantum Mechanical-Derived Versus General-Purpose Force Fields Tested on a Luminescent Iron Complex

“…For instance, in the case of the much more solvent-dependent Ru(II)-polypyridine complex surrounded by dimethyl sulfoxide (DMSO) the first solvent shell is located at ca. 5.5 Å from the metal [76]. functions gαβ (rαβ) defined between specific solute (α) and solvent (β) atoms.…”

“…Here we evaluate and discuss the merits and shortcomings of these two striking opposite strategies by comparing the accuracy of a general-purpose, transferable, FF and a specifically tailored QMD-FF in predicting both the ground state structure and the room temperature Uv-Vis absorption of the octahedral Iron(III) complex with two phtmeimb ligands, were phtmeimb stands for [phenyl(tris(3-methylimidazol-1-ylidene))borate] -(see Figure 1), recently reported by Wärnmark and co-workers [37,84], showing nanosecond ligand-to metal charge-transfer (LMCT) lifetime. For the definition of the QMD-FF, among others [69,[71][72][73][74][75][77][78][79], we here resort to the JOYCE protocol [78,85,86], already successfully employed to study the solvation features of octahedral TMCs [76,87], based on higher-level QM descriptors. Turning to the general-purpose FF, as an example of a transferable black-box approach, the standard General Amber Force Field (GAFF) method [88] was adopted whenever possible, by transferring all bonded FF parameters from the proper GAFF database, while retrieving the missing parameters (involving the metal and Boron sites) from supplementary literature databases, as described in section 3.1.2.…”

Electronic Properties of Electron-Deficient Zn(II) Porphyrins for HBr Splitting

“…All calculations were performed with Gaussian 09 [23]. Ground state structures of 1 and 2 were optimized at the B3LYP/DGDZVP level [24] in vacuo. Singlet electronic transitions were computed on the optimized geometries at the TDDFT/B3LYP/6-311G d,p level in toluene treated as a dielectric continuum (IEFPCM).…”

Optical properties of photodynamic therapy drugs in different environments: the paradigmatic case of temoporfin

“…However, the sensitivity of excited state properties to even the slightest structural modifications also requires careful parameterization of the force fields. [67][68][69] In this study, we report the optical and photophysical properties of mTHPC employing molecular simulations in different environments: (a) in vacuo, (b) in solution, (c) in solution encapsulated within TM-b-cyclodextrin (mTHPC:TM-b-CD complex), and (d) in interaction with a lipid bilayer mimicking a biological membrane. Herein, we provide a clear rationalization of the optical properties of the most relevant PDT drug; the coupling between its critical structural parameters, the degrees of freedom of different molecular environments, such as drug delivery systems or cellular compartments, and the effects of heterogeneous environments on its photophysical properties.…”