Dithiocarbamate Ligands Research Articles

A series of red iridium(iii) complexes using flexible dithiocarbamate derivatives as ancillary ligands for highly efficient phosphorescent OLEDs

Five red iridium(iii) complexes with dithiocarbamate ligands were investigated, and their OLEDs exhibit an EQEmax of 20.69% with low efficiency roll-off.

Rapid room temperature synthesis of red iridium(iii) complexes containing a four-membered Ir-S-C-S chelating ring for highly efficient OLEDs with EQE over 30.

Three red cyclometalated iridium(iii) complexes (4tfmpq)2Ir(dipdtc), (4tfmpq)2Ir(dpdtc) and (4tfmpq)2Ir(Czdtc) (4tfmpq = 4-(4-(trifluoromethyl)phenyl)quinazoline, dipdtc = N,N-diisopropyl dithiocarbamate, dpdtc = N,N-diphenyl dithiocarbamate, and Czdtc = N-carbazolyl dithiocarbamate) containing the unique four-membered Ir-S-C-S backbone ring were synthesized in five minutes at room temperature with good yields, and the Gibbs free energy calculation results indicate that all reactions are exothermic and thermodynamically favorable processes. The emission colors (λ peak = 641-611 nm), photoluminescence quantum efficiencies (Φ P = 58.3-93.0%) and bipolar properties can be effectively regulated by introducing different electron-donating substituents into the dithiocarbamate ancillary ligands. Employing these emitters, organic light emitting diodes (OLEDs) with double emissive layers exhibit excellent performances with a maximum brightness over 60 000 cd m-2, a maximum current efficiency of 40.68 cd A-1, a maximum external quantum efficiency (EQEmax) of 30.54%, and an EQE of 26.79% at the practical luminance of 1000 cd m-2. These results demonstrate that Ir(iii) complexes with sulfur-containing ligands can be rapidly synthesized at room temperature, which is key to the production of metal luminescent materials for large-scale application in highly efficient OLEDs.

A new structural motif for cadmium dithiocarbamates: crystal structures and Hirshfeld surface analyses of homoleptic zinc and cadmium morpholine dithiocarbamates

Abstract The crystal and molecular structures of two homoleptic morpholine-derived dithiocarbamates of zinc, binuclear {Zn[S2CN(CH2CH2)2O)2]2}2 (1), and cadmium, one-dimensional coordination polymer {Cd[S2CN(CH2CH2)2O)2]2}2 (2), are described. In 1, a centrosymmetric binuclear molecule is found as there are equal numbers of chelating and bidentate bridging dithiocarbamate ligands; weak transannular Zn···S interactions are found within the resultant eight-membered {···SCSZn}2 ring which has the form of a chair. The resultant 4+1 S5 donor set is highly distorted with the geometry tending towards a square-pyramid. By contrast, a square-planar geometry is found in centrosymmetric 2 defined by symmetrically chelating dithiocarbamate ligands. The presence of Cd···S secondary bonding in the crystal of 2 leads to a distorted 4+2 S6 octahedron and a linear coordination polymer, which is unprecedented in the structural chemistry of cadmium dithiocarbamates. The analyses of the Hirshfeld surfaces for 1 and 2 show the dominance of H···H, S···H/H···S and O···H/H···O contacts to the surface, i.e. contributing around 90 and 80%, respectively.

Tris(N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamato-S,S′)cobalt(III) for anion sensing and preparation of cobalt-iron sulfide nanoparticles: A new photocatalyst for the degradation of dyes

Tris(N-(pyrrol-2-ylmethyl)-N-butyldithiocarbamato-S,S′)cobalt(III) (1) and tris(N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamato-S,S′)cobalt(III) (2) have been synthesized and characterized by elemental analysis and spectroscopy (IR, UV-vis and NMR). The elemental analysis and IR, 1H and 13C NMR spectra are consistent with the formation of the cobalt(III) complexes with dithiocarbamate ligands. The anion binding properties of 1 and 2 based on host-guest interaction have been examined with the use of cyclic voltammetry.This study showed that both complexes preferred to bind with I-compared to other halides. 2 has been used as precursors for the preparation of cobalt-iron sulfide nanoparticles. TEM image of cobalt-iron sulfide nanoparticles showed that the particles are spherical. The elemental compositions of the nanoparticles were confirmed by energy dispersive X-ray spectroscopy. IR spectral studies on nanoparticles confirm the presence of capping agent (triethylenetetramine). The nanoparticles were explored as photocatalysts to study the degradation of dyes using methylene blue and rhodamine-B in aqueous solution under UV irradiation. The cobalt-iron sulfide works as an efficient photocatalyst for degradation of rhodamine-B.

Energy level tuning of InP/ZnS nanocrystals by electronically delocalized dithiocarbamate derivatives

The nanocrystals have characteristics of varying the energy gap between the valence band and the conduction band depending on the size, and are attracting attention as light emitting materials due to the excellent in light stability. Since the bandgap of nanocrystals is determined by the size, it is very important to control the size of the nanocrystals in order to realize the red, green and blue primary color in a display. However, there are many difficulties in finely adjusting the nanocrystal bandgap to a size. In this study, the monodentate amine ligands coordinated on the surface of InP/ZnS nanocrystals are substituted with bidentate dithiocarbamate ligands having a strong coordination ability and electrically resonant structures, so that the nanocrystal can be finely tuned to control the emission spectrum. NMR analysis showed that some amine ligands on the surface of the nanocrystals were substituted with dithiocarbamate ligands. The PL spectra also show that the emission wavelength of the new nanocrystals is increased by about 20 nm (bathochromic shift), indicating that the active region of the exciton (an electron-hole pair) is extended to the delocalized dithiocarbamate ligands as well as the nanocrystals.

Group 10 metal complexes of dithiocarbamates derived from primary anilines: Synthesis, characterization, computational and antimicrobial studies

Dithiocarbamate ligands obtained from primary amines, namely N-phenylaniline, 4-methylaniline and 4-ethylaniline, and represented as L1, L2 and L3 respectively, have been used to prepare some Ni(II), Pd(II) and Pt(II) complexes. The complexes were characterized by NMR, FTIR spectroscopy and elemental analysis. The spectroscopic data showed that the ligands were chelated to the metal ions in a bidentate mode. The complexes [Pt(L1)2], [Pt(L3)2], and [Pd(L1)2] were further characterized by single crystal X-ray analysis and distorted square planar geometries were confirmed in all cases. The magnetic susceptibility measurements of the nickel complexes suggest a square planar geometry for the diamagnetic compounds. Thermal decomposition studies of the complexes gave their respective metal sulfides as residues. Geometry optimization and harmonic frequency calculations of the ligands and the complexes were carried out using density functional theory (DFT). Molecular electrostatic potential energy calculations were used to support the coordination through the dithio-sulfur groups of the three dithiocarbamate ligands. Non-covalent interaction (NCI) theory analysis was used to reveal the different intra and intermolecular interactions in the hydrogen bonded structures of the platinum and palladium complexes. Antimicrobial screening, conducted using selected microbes, showed that the complexes gave moderate to very active antimicrobial activities against Gram negative (Escherichia coli, Klebsiella pneumonia and Pseudomonas aeruginosa), Gram positive (Bacillus cereus and Staphylococcus aureus) and fungi (Candida albicans and Aspergillus flavus) organisms at a concentration of at 50 μg/mL. However, the [Pt(L3)2] complex gave the best antimicrobial properties with an inhibitory zone range of 8–26 mm.

SiRNA Delivery Using Dithiocarbamate-Anchored Oligonucleotides on Gold Nanorods.

We present a robust method for loading small interfering RNA (siRNA) duplexes onto the surfaces of gold nanorods (GNRs) at high density, using near-infrared laser irradiation to trigger their intracellular release with subsequent knockdown activity. Citrate-stabilized GNRs were first coated with oleylsulfobetaine, a zwitterionic amphiphile with low cytotoxicity, which produced stable dispersions at high ionic strength. Amine-modified siRNA duplexes were converted into dithiocarbamate (DTC) ligands and adsorbed onto GNR surfaces in a single incubation step at 0.5 M NaCl, simplifying the charge screening process. The DTC anchors were effective at minimizing premature siRNA desorption and release, a common but often overlooked problem in the use of gold nanoparticles as oligonucleotide carriers. The activity of GNR-siRNA complexes was evaluated systematically against an eGFP-producing ovarian cancer cell line (SKOV-3) using folate receptor-mediated uptake. Efficient knockdown was achieved by using a femtosecond-pulsed laser source to release DTC-anchored siRNA, with essentially no contributions from spontaneous (dark) RNA desorption. GNRs coated with thiol-anchored siRNA duplexes were less effective and also permitted low levels of knockdown activity without photothermal activation. Optimized siRNA delivery conditions were applied toward the targeted knockdown of transglutaminase 2, whose expression is associated with the progression of recurrent ovarian cancer, with a reduction in activity of >80% achieved after a single pulsed laser treatment.

Synthesis, structural and antimicrobial studies of binary and ternary complexes of a new tridentate thiosemicarbazone.

A new thiosemicarbazone ligand was synthesized and characterized using spectroscopic techniques (UV-Vis and IR) and synchrotron x-ray powder diffraction. With M2+=Mn2+, Zn2+ and Cd2+, coordination compounds of the type (M[L]2) were isolated. In the presence of sodium dithiocarbamate salts (NadiEtdtc.3H2O=sodium diethyldithiocarbamate trihydrate and Napipdtc=sodium piperidinedithiocarbamate), Zn2+ and Cd2+ were able to form ternary octahedral complexes where each metal binds a deprotonated (thiosemicarbazone) ligand, a monobasic dithiocarbamate ligand and a water molecule. In vitro biological evaluation tests of the free HL ligand and its metal complexes against selected fungal and bacterial cultures were performed. Compared with HL, the complexes displayed enhanced biological activities and ternary Zn (II) complexes displayed comparable antibacterial activities to the chloramphenicol standard.

Conversion of Dithiocarbamate Ligand into Sulphate Anion : Spectroscopy, X-ray Crystallography and Valence Bond Sum (VBS) Based Investigations

Conversion of Dithiocarbamate Ligand into Sulphate Anion : Spectroscopy, X-ray Crystallography and Valence Bond Sum (VBS) Based Investigations

Sulphur Ligand Functionalized Carbon Nanotubes for Removal of mercury from waste water – experimental and density functional theoretical study

ABSTRACTOwing to the strong interaction of mercury with sulphur, thiol(SH) and dithiocarbamate (DTC) ligands were grafted on multi-walled carbon nanotubes (MWCNTs) and were characterized by elemental analysis, SEM-EDS, FTIR, and XRD analysis. The maximum adsorption capacity of MWCNT-DTC was found to be 3.5 times higher than that of MWCNT-SH at the optimum pH of 6. The kinetics and equilibrium data revealed that the adsorption of Hg2+ follow pseudo-first-order and Langmuir isotherm model, respectively. Density functional theoretical calculation performed for the interaction of Hg2+ ion with SWCNT-DTC and SWCNT-SH corroborated the experimental output that former have greater adsorption than the later.Test- L2

Synthesis, characterization and cytotoxic activity of vanadocene dithiocarbamate complexes

This study describes synthesis of water-soluble vanadocene and 1,1′-dimethylvanadocene compounds bearing dithiocarbamate ligands. All prepared compounds were characterized by analytical and spectroscopic methods. The structure of [(η5-C5H4Me)2V{S2CN(CH2)4O}]Cl was determined by single-crystal X-ray diffraction analysis. The cytotoxicity of the synthesized compounds was investigated on human leukemia cells MOLT-4. The derivatives bearing cyclic dithiocarbamates show considerably stronger activity than reported for cisplatin.

Proteasome versus Thioredoxin Reductase Competition as Possible Biological Targets in Antitumor Mixed Thiolate-Dithiocarbamate Gold(III) Complexes.

New mixed gold(III) derivatives with dithiocarbamate and thiolate ligands have been synthesized and characterized. They display high anticancer activity against colon cancer cell lines without affecting to differentiated enterocytes, high stability in phosphate-buffered saline solution, and resistance to gold reduction in the presence of reducing agents in the majority of the derivatives. Some of them show interaction with thioredoxin reductase as derived from in vitro analysis and computational studies. However, a competition between this enzyme and proteasome is detected in cells, which is corroborated by the determination of proteasomal chymotrypsin-like activity inhibition. In addition, some of these dithiocarbamate gold(III) derivatives reduce cell viability and proliferation by intrinsic apoptotic pathway, with changes in mitochondrial membrane potential, cytochrome c release and caspase-3 activation. Consequently, our results show new complexes with proteasome as possible target in colorectal cancer.

A Simple Route to Ruthenium Sulfide Nanoparticles via Thermal Decomposition of Precursor Complexes

The research work presented here investigate the use of homonuclear tris-dithiocarbamato ruthenium(III) complexes as single-source molecular precursors to ruthenium sulfide nanoparticles. The dithiocarbamate ligands with their respective precursor complexes were characterized by UV-Vis, FTIR, 1H- and 13C-NMR, and in addition TGA was used for precursors. The absorption spectra confirmed the geometry of tris-chelate ruthenium complexes [Ru(S2CNR2)3] to be octahedral and were very stable both in solution and in the solid state. The optical and structural properties of the ruthenium sulfide nanoparticles were examined using FTIR, XRD, EDS, SEM, TEM, UV-Vis and photoluminescence (PL). FTIR studies revealed that Ru2S3 nanoparticles are capped through the interaction of the –NH2 group of hexadecylamine (HDA) adsorbed on the surfaces of nanoparticles with the prominent band observed around 3330 cm-1 due to v(N-H). The XRD confirmed the successful formation of ruthenium sulfide nanoparticles with a cubic crystal structure within the nano-scale range. The optical band gap(Eg) determined from Tauc plot was found in the range (3.44 to 4.18 eV) values.

Stabilization of Silver Nanoparticles with a Dithiocarbamate Ligand and Formation of Nanocomposites by Combination with Polythiophene Derivative Nanoparticles

Spherical morphology for silver nanoparticles (Ag NPs) stabilized with dithiocarbamate (DTC) by reducing silver nitrate with sodium borohydride was obtained, while the addition of sodium citrate and hydrogen peroxide allowed the formation of silver nanotriangles (Ag NTs). Solutions of bright yellow and blue colors characteristic of both morphologies were observed. UV-vis optical analysis of NPs stabilized with DTC showed a plasmonic absorption band at 393 nm characteristic for spherical morphology, while two bands were observed at 332 nm and 762 nm, and a shoulder around 500 nm for the triangular morphology; with these spectra each morphology was confirmed. In these spectra an absorption band between 250 and 260 nm confirms the presence of DTC ligand. The stability of the NPs was achieved using an 8.69 × 10-3 mM solution of 4-(ethylaminodithiocarbamate) methylpyridine di-n-butyltin (IV) through a transmetallation reaction. Silver nanoparticles (Ag NPs) with spherical morphology of average diameter of 12.7 ± 1.2 nm and triangular morphology with 28.9 ± 0.8 nm for each side of the triangles were analyzed by high resolution scanning electron microscopy (HR-SEM). UV-vis spectra also showed the stability of NPs with DTC for more than three months. A copolymer derived of 3-hexylthiophene with (E)-2-(ethyl(4-((4-nitrophenyl) diazenyl) phenyl) amino) ethyl 2-(thiophen-3-yl) acetate (PA) was tested to get polymer NPs by reprecipitation method using THF/water systems. PA Polymer NPs having average diameter of 9.0 ± 1.7 nm were found. By quick and easy procedure, the formation of nanocomposite (NC) of spherical Ag NPs and PA polymer NPs was reached. This NC could be used as imaging agent, electrochemical biosensor, and photonic and optoelectronic device materials.

SYNTHESIS, CHARACTERIZATION AND FUNGICIDAL POTENTIALITIES OF SOME TRANSITION METAL COMPLEXES OF BENZIMIDAZOLEDITHIOCARBAMATE BASED LIGAND

New substituted benzimidazole dithiocarbamate ligand (HL) and a set of its transition metal complexes were synthesized and characterized based on the elemental analyses, IR, MS, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA and DrTG). From the obtained IR data, HL is a neutral tridentate ligand and its complexes were proposed to have the general formulae [MCl(HL)(H2O)2]Cl2.2H2O (M = Cr(III) and Fe(III)] and [MCl(HL)(H2O)2]ClyH2O (for y = 2: M = Mn(II), Co(II) and Cu(II) and for y = 1: M = Ni(II), Zn(II) and Cd(II)). The molar conductance data revealed that all the metal chelates were electrolytes. From the magnetic and solid reflectance spectra, it was found that the geometrical structure of the synthesized complexes is octahedral. The thermal behaviour of these chelates showed that the hydrated complexes loss water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. Fungicidal activity of the new ligand and its related complexes was evaluated against three soil-borne fungi that cause many destructive diseases as damping off, root and stem rots of many plants. The tested fungi are Fusarium solani, Rhizoctonia solani and Sclerotium rolfesii. Data obtained showed that introducing an electron-withdrawing nitro group in position (5) of benzimidazole ring enhanced the biological potentialities of the parent ligand and some of its transition metal chelates to show better activity than the standard fungicide Pencycuron.

Synthesis and Characterization of Palladium (II) Complexes Containing Mixed Ligands with Pyrrolidine Dithiocarbamate and Phosphines

This work includes preparation and characterization of new four mono nuclear complexes of palladium metal ion result from treating palladium chloride with ammonium pyrrolidine dithiocarbamate (PDTC), tertiary phosphines(dppe, dppp) and 2-phenyl pyridine (Hppy) in different molar ratios. All complexes have been characterized by spectroscopic methods{IR, UV-Vis, 1HNMR} spectroscopy, in addition to elemental analysis (C.H.N) and conductivity measurement. pyrrolidine dithiocarbamate‎ ligand behaves like bidentate in the complexes [Pd(PDTC)(dppe)]Cl and [Pd(PDTC)(ppy)] but it behaves as mono dentate in the complexes [Pd(PDTC)2(dppp)] and [Pd(PDTC)2(dppe)], while tertiary phosphines and 2-phenyl pyridine behave like bidentate ligand.

Synthesis, characterization and anticancer studies of bis(1-phenylpiperazine dithiocarbamato) Cu(II), Zn(II) and Pt(II) complexes: Crystal structures of 1-phenylpiperazine dithiocarbamato-S,S′ zinc(II) and Pt(II)

Copper(II), zinc(II) and platinum(II) complexes of phenylpiperazine dithiocarbamate formulated as [CuL2], [PtL2] and [Zn2(μ-L)2(L)2], where L = phenylpiperazine dithiocarbamate were prepared and characterized by elemental analysis IR, UV–Visible, 1H and 13C NMR spectroscopy. Single crystal X-ray structures of the Zn(II) and Pt(II) complexes are also reported. The FTIR spectra of the complexes confirm the bidentate coordination of the ligand to the metal ions by the single band due to ν(CS) observed in the range 1012–1014 cm−1 compared to that of the ligand at 994 cm−1. Electronic spectra of both the Cu(II) and Pt(II) complex are consistent with square planar geometry, this is further confirm in the case of the Pt(II) complex by the single X-ray crystal structure. The molecular structure of the Zn(II) complex indicate a centrosymmetric dimeric compound in which each of the zinc ion is bonded to two molecules of the ligands acting as either bidentate chelating or as bridging coordinating ligand resulting in a distorted octagonal cycle comprising of two zinc ions, two thioureide carbons and four sulphur atoms. The geometry around each zinc ion is a distorted tetrahedral geometry. The Pt(II) complex consist of a monomeric entity where the Pt(II) ion is surrounded by four sulphur donor atoms from the two phenylpiperazine dithiocarbamate ligands forming a slightly distorted square planner geometry around the Pt(II) ion. Anticancer potency of the complexes against three cancer cell lines indicates UACC62 > MCF7 > TK10 at IC50 values of 3.34, 17.52 and 19.83 μM respectively for the Cu(II) complex. MCF7 > TK10 > UACC62 at IC50 of 8.42, 13.40 and 15.14 μM respectively for Zn(II), whereas for the Pt(II) the activity stands at concentration (IC50) >100 μM for all the cell lines.

Structural variations in zinc(II) complexes with N,N-di(4-fluorobenzyl)dithiocarbamate and imines: New precursor for zinc sulfide nanoparticles

Bis(N,N-di(4-fluorobenzyl)dithiocarbamato-κ2S,S′)zinc(II) (1), bis(N,N-di(4-fluorobenzyl)dithiocarbamato-κ2S,S′)(pyridine-κN)zinc(II) (2), (μ-4,4′-bipyridine-κ2N,N′)bis[bis(N,N-di(4-fluorobenzyl)dithiocarbamato-κ2S,S′)zinc(II)] (3) and (2,2′-bipyridine-κ2N,N′)bis(N,N-di(4-fluorobenzyl)dithiocarbamato-κS,S′)zinc(II) (4) were prepared and characterized by elemental analysis, spectroscopy (IR, 1H and 13C NMR) and their structures were elucidated by X-ray crystallography. The centrosymmetric dinuclear structure of 1 features both bridging and chelating dithiocarbamate ligands to that a distorted trigonal bipyramidal S5 coordination geometry results. The coordination geometry of zinc(II) in 2 and both zinc(II) in the dinuclear complex 3 is an intermediate between tetragonal pyramidal and trigonal bipyramidal. In complex 4, the resulting N2S4 donor set defines a distorted octahedral geometry. Addition of imines (pyridine, 4,4′-bipyridine and 2,2′-bipyridine) to the complex 1 affects the ZnS distances and SZnS angles. The optimized geometry, HOMO-LUMO in the ground state and MEP have been calculated for 1 and 2. MEP analysis support the substantial contribution of the resonance structure RR′-N+CS22− to the description of their structures on the complexes 1 and 2. Quantification of the intermolecular interactions present in 1–4 was realized by Hirshfeld surface analysis. Zinc sulfide nanoparticles were prepared from 1 and characterized by PXRD, SEM, TEM, EDAX and DRS. The PXRD study showed that the nanoparticles is composed of cubic phase of zinc sulfide. Photocatalytic activity of as-prepared ZnS was tested by examining the degradation of rhodamine-B in aqueous solution under UV light illumination.

Crystal structures and Hirshfeld surface analyses of (N-hexyl-N-methyl-dithio-carbamato-κ2S,S')triphenyl-tin(IV) and [N-methyl-N-(2-phenyl-ethyl)-dithio-carbamato-κ2S,S']tri-phenyl-tin(IV).

The crystal and mol-ecular structures of two tri-phenyl-tin di-thio-carbamate compounds, viz. [Sn(C6H5)3(C8H16NS2)], (I), and [Sn(C6H5)3(C10H12NS2)], (II), are described. The di-thio-carbamate ligand in each mol-ecule coordinates in an asymmetric fashion resulting in heavily distorted tetra-hedral C3S coordin-ation geometries for the Sn atoms, with the distortions traced to the close approach of the non-coordinating thione-S atom. The mol-ecular packing in both compounds features C-H⋯π(Sn-phen-yl) inter-actions. In (I), the donors are Sn-phenyl-C-H groups leading to centrosymmetric aggregates, while in (II), the donors are both Sn-phenyl-C-H and methyl-C-H groups leading to supra-molecular chains propagating along the b axis. The identified aggregates assemble into their respective crystals with no directional inter-actions between them. An analysis of the Hirshfeld surfaces show distinctive patterns, but an overwhelming predominance (>99% in each case) of H⋯H, C⋯H/H⋯C and S⋯H/H⋯S contacts on the respective Hirshfeld surface.

C[sbnd]H⋯Ni and C[sbnd]H⋯π(chelate) interactions in nickel(II) complexes involving functionalized dithiocarbamates and triphenylphosphine

New bis(N-benzyl-N-substituted benzyldithiocarbamato-S,S′)nickel(II) (1–3) and (N-benzyl-N-substituted benzyldithiocarbamato-S,S′)(isothiocyanato-N)- (triphenylphosphane)nickel(II) (4–6) [where substituted benzyl = 2-HOC6H4CH2 (1,4), 3-HOC6H4CH2 (2,5), 4-FC6H4CH2 (3,6)] were synthesized and characterized using IR, electronic, and NMR (1H and 13C) spectra. X-ray structural analysis of homoleptic complex (1) and heteroleptic complexes (5 and 6) confirmed the presence of four coordinated nickel in a distorted square planar arrangement with NiS4 and NiS2PN chromophores, respectively. The νC–S stretching vibrations are observed around 990 cm−1 without any splitting supporting the bidentate coordination of the dithiocarbamate ligand. Electronic spectral studies of all the complexes (1–6) indicate that the geometry of the nickel atom is probably square planar. NMR spectra of all homoleptic and heteroleptic complexes (1–6) reveal a weak signal associated with the backbone carbon (N13CS2) in the region 204.0–210.0 ppm with a weak intensity characteristic of the quaternary carbon signals. The greater trans influence of triphenylphosphine in complexes 5 and 6 is supported by the long NiS distance compared to other NiS distance which is opposite to the NCS− ligand. In the structure of complex 5, C–H⋯π(chelate) interactions results in polymeric chain. Both structures show intramolecular Ni⋯H interactions but that on 6 is the strongest. C–H⋯π interactions are also found in 1, 5 and 6. Hirshfeld surface analysis and the associated 2D fingerprint plots of 1, 5 and 6 have been studied to evaluate intermolecular interactions. The molecular geometries of complexes 1, 5 and 6 have been optimized by abinitio HF method using LANL2DZ program.