Latest Publications

DOI: 10.1021/jacs.9b12464

Journal of the American Chemical Society

Due to the great potential expressed by an anticancer drug candidate previously reported by our group, namely, Ru-sq ([Ru(DIP)2(sq)](PF6) (DIP, 4,7-diphenyl-1,10-phenanthroline; sq, semiquinonate ligand), we describe in this work a structure–activity relationship (SAR) study that involves a broader range of derivatives resulting from the coordination of different catecholate-type dioxo ligands to the same Ru(DIP)2 core. In more detail, we chose catechols carrying either an electron-donating group (EDG) or an electron-withdrawing group (EWG) and investigated the physicochemical and biological properties of their complexes. Several pieces of experimental evidences demonstrated that the coordination of catechols bearing EDGs led to deep-red positively charged complexes 1–4 in which the preferred oxidation state of the dioxo ligand is the uninegatively charged semiquinonate. Complexes 5 and 6, on the other hand, are blue/viol...

DOI: 10.1021/jacs.9b12762

ACS Publications

Molecular-level multielectron handling toward electrical storage is a worthwhile approach to solar energy harvesting. Here, a strategy which uses chemical bonds as electron reservoirs is introduced to demonstrate the new concept of “structronics” (a neologism derived from “structure” and “electronics”). Through this concept, we establish, synthesize, and thoroughly study two multicomponent “super-electrophores”: 1,8-dipyridyliumnaphthalene, 2, and its N,N-bridged cyclophane-like analogue, 3. Within both of them, a covalent bond can be formed and subsequently broken electrochemically. These superelectrophores are based on two electrophoric (pyridinium) units that are, on purpose, spatially arranged by a naphthalene scaffold. A key characteristic of 2 and 3 is that they possess a LUMO that develops through space as the result of the interaction between the closely positioned electrophoric units. In the context of electron storage, this “super-LUMO...

DOI: 10.1002/jcc.26170

Journal of Computational Chemistry

In this paper we present the implementation and benchmarking of a Time Dependent Density Functional Theory approach in conjunction with Double Hybrid (DH) functionals. We focused on the analysis of their performance for through space charge‐transfer (CT) excitations which are well known to be very problematic for commonly used functionals, such as global hybrids.Two different families of functionals were compared, each of them containing pure, hybrid and double‐hybrid functionals.The results obtained show that, beside the robustness of the implementation, these functionals provide results with an accuracy comparable to that of adjusted range‐separated functionals, with the relevant difference that for DHs no parameter is tuned on specific compounds thus making them more appealing for a general use. Furthermore, the algorithm described and implemented is characterized by the same computational cost scaling as that of the ground sta...

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