Synthesis and Physico-Chemical Properties of Homoleptic Copper(I) Complexes with Asymmetric Ligands as a DSSC Dye

To develop low-cost and efficient dye-sensitized solar cells (DSSCs), we designed and prepared three homoleptic Cu(I) complexes with asymmetric ligands, M1, M2, and Y3, which have the advantages of heteroleptic-type complexes and compensate for their synthetic challenges. The three copper(I) complexes were characterized by elemental analysis, UV-vis absorption spectroscopy, and electrochemical measurements. Their absorption spectra and orbital energies were evaluated and are discussed in the context of TD-DFT calculations. The complexes have high VOC values (0.48, 0.60, and 0.66 V for M1, M2, and Y3, respectively) which are similar to previously reported copper(I) dyes with symmetric ligands, although their energy conversion efficiencies are relatively low (0.17, 0.64, and 2.66%, respectively).

DFT Studies and Molecular Dynamics of the Molecular and Electronic Structure of Cu (II) and Zn (II) Complexes with the Symmetric Ligand (Z)-2-((3,5-dimethyl-2H-pyrrol-2-yl) methylene)-3,5-dimethyl-2H-pyrrole

The binding patterns of the metal cations Cu 2+ and Zn 2+ with the symmetric ligands (Z)-2-((3,5-dimethyl-2H-pyrrol-2-yl) methylene)-3,5-dimethyl-2H-pyrrole (L1) and (Z)-2-(1-(3,5-dimethyl-2H-pyrrol-2-yl)ethylidene)-3,5-dimethyl-2H-pyrrole (L2), have been investigated at B3LYP and MM2 level of theories in the gas phase and a solution respectively. Natural bond orbital (NBO) analysis has been applied to explore the character of metal-ligand coordination. The stability of the most favorable binding motifs of the metal ions has also been investigated by the molecular dynamics (MD) simulation. Finally, the inhibition activity of the complexes (L1Cu2+), (L2Cu2+), (L1Zn2+), and (L2Zn2+) against the DNA dependent protein kinase also have been investigated by molecular docking studies.

MOFs assembled from C3 symmetric ligands: structure, iodine capture and role as bifunctional catalysts towards the oxidation–Knoevenagel cascade reaction

Three new NiII/CoII-based MOFs constructed from C3 symmetric H3BTC and 4-TPT ligands have been characterized. MOF3 as a bifunctional acid−base catalyst showed good activities for the oxidation–Knoevenagel cascade reaction.

Cathecol and Naphtol Groups in Salphen-Type Schiff Bases for the Preparation of Polynuclear Complexes

In this paper, we show a strategy to modify salphen-type Schiff base ligands with naphtol (SYML1) and pyrocathecol (2,3-dihydroxyphenyl) groups (SYML2), or a combination of both (ASYML). Each of these ligands can be used to obtain polynuclear metal complexes following two different strategies. One relies on using metals that are either too large for the N2O2 cavity or not fond of coordination number 4 and the other one relies on forcing the polynuclear species by adding functional groups to the hydroxybenzaldehayde in order to have extra coordination sites in the ligand. We report and characterize the mononuclear complexes SYML1-Cu and SYML1-Ce, along with the dinuclear complex SYML1-Fe and the tetranuclear species SYML2-Mn. The asymmetric ligand ASYML routinely hydrolyzes into the symmetric ligands in the reaction mixtures. SYML1-Fe displays a nearly linear Fe-O-Fe bridge with very strong antiferromagnetic coupling between the Fe(III) ions.

Supramolecular chirality transformation driven by monodentate ligand binding to a coordinatively unsaturated self-assembly based on C3-symmetric ligands

A supramolecular chirality transition driven by monodentate ligand binding, the present strategy shows promise for the rational design of dynamic coordination chirality capable of alternating between chiral objects of different shapes driven by a specific external stimulus.