Geometrical structure, electronic and nonlinear optical properties of square‐planar heteroleptic complexes containing bypridine and pyrazine dithiolate derivatives as dye‐sensitized solar cell: A DFT study

Abstract

The structural stability, optoelectronic and nonlinear optical (NLO) properties of the designed heteroleptic complexes [M (diimine)(dithiolate)] {M = Ni, Pd and Pt; diimine = 2,2′-bipyridine (bpy); dithiolate = pyrazine-2,3-dithiolate (pdt), uinoxaline-2,3-dithiolate (qdt) and 2,5-dicyano-2,3-dithiolatepyrazine (dcdmp)} were determined by means of the density functional theory (DFT) method and time-dependent-DFT calculations. Natural bond orbital analyses are also performed for scrutinizing the structural properties of the considered heteroleptic complexes. This study compared the sensitization properties of all complexes in terms of their electronic properties, such as molecular orbital distribution, gap energy (E g ), absorbed wavelength (λ max ), light-harvesting efficiency (LHE), charge transfer descriptors, dipole moment (μ), polarizability (α) and first hyperpolarizability (β 0 ). Based on the obtained results, it can be induced that the change of metal center and dithiolate ligands plays a key role in tuning optoelectronic properties, especially the LHE and hyperpolarizability.Also the results reveal that Pt as metal center with qdt ligand considerably increases their electronic and NLO properties. Moreover, the thermodynamic analysis showed that the formation of these complexes is exothermic, and the synthesis of all considered complexes will be possible at 298 K and 1 atm. To sum up, it seems that these designed complexes could be introduced as promising new electro-optical materials.

Ni, Pd, and Pt complexes of a tetradentate dianionic thiosemicarbazone-based O^N^N^S ligand

“…However, this seemingly deviating ordering has been observed before along the d 8 triade and is usually explained in terms of energy matching of the metal-borne binding orbitals in the case of Ni and Pt. 36,[43][44][45][46] The low-energy tailing of these bands reveals additional weaker transitions in the case of Ni and Pt which extend to λ = 650 nm. Based on the similarity to the recently studied Pt(II) complexes of the pyridinecarbaldehyde (S)-N4-(α-methylbenzyl)thiosemicarbazone (HTSCmB) ligands, 35 these broad bands are preliminarily assigned to metal-to-ligand charge transfer (MLCT) transitions.…”

Stereoselective synthesis of oxime containing Pd(ii) compounds: highly effective, selective and stereo-regulated cytotoxicity against carcinogenic PC-3 cells

“…23–34 As a part of an ongoing research project, we have used enantiopure amino-oxime pro-ligands derived from commercially available and low-cost natural terpenes 35,36 to prepare a variety of water-soluble, enantiopure Ru( ii ), Ti( iv ), Pd( ii ) and Pt( ii ) compounds that have already demonstrated the great potential of this approach in the design of novel anticancer metallodrugs. 37–40 Other oxime metal compounds have also been reported to have interesting antitumor properties and different DNA interactions from those of cisplatin (see for example Pt, 41–47 Pd, 48–51 Rh, Ir, 52–54 and Ru 53,55–58 ). Regarding Pd( ii ) coordination chemistry, oxime groups are excellent ligands for stabilization purposes, with a wide versatility of coordination modes going from mono-κN, 59 -κO 42 to di-hapto κ 2 N,O either with side on or bridging coordination.…”

Heteroleptic Pd(II) and Pt(II) Complexes with Redox-Active Ligands: Synthesis, Structure, and Multimodal Anticancer Mechanism

“…Upon replacement of chlorido ligands with dithiolates, Pt II and Pd II typically form “push–pull” complexes of the [M­(diimine)­(dithiolate)] type. − We used complexes 1 and 4 as starting materials for the synthesis of heteroleptic complexes [M­(dpp-Bian)­(dmit)] (M = Pd ( 2 ), Pt ( 5 )) and [M­(dpp-Bian)­(dsit)] (M = Pd ( 3 ), Pt ( 6 )) (Scheme ). They were obtained by reaction of 1 and 4 with (NBu 4 ) 2 [Zn­(dsit) 2 ] or (NBu 4 ) 2 [Zn­(dmit) 2 ] as crystalline green powders in 95–99% (for Pd) and 50–58% (for Pt) yields and characterized by FT-IR and 1 H NMR spectroscopy.…”