A novel beta-polymorph of mercury(II) di-iso-butyldithiocarbamate (Hg(II)-(i)Bu(2)Dtc) was prepared and successfully characterised using solid-state C-13 and N-15 CP-MAS NMR spectroscopy, single-crystal XRD analysis, FT-IR spectroscopy and simultaneous (TG/DSC) thermal analysis (STA). The resulting polymorphic phase is characterised by a rather rare crystal structure, which reveals the coexistence of alternated mononuclear, [Hg((S2CNBu2)-Bu-i)(2)], and binuclear, [Hg-2((S2CNBu2)-Bu-i)(4)], molecular forms of the complex in a ratio of 1:1. Therefore, in each of the experimental C-13 and N-15 CP-MAS NMR spectra of the polymorph, the chemical >NC(S)S- groups are represented by three resonance signals of equal integral intensities, indicating three groups of inequivalent (i)Bu(2)Dtc ligands. Moreover, their C-13 and N-15 chemical shift values support either terminal chelating or tridentate bridging structural functions for these dithiocarbamate ligands. According to the experimental data of energy dispersive X-ray (EDX) spectroscopy and STA, thermolysis of di-iso-butyldithiocarbamate mercury(II) complex yields HgS as a single end-product.

New crystalline pseudo-polymer complex [AuS2CN(CH2)62]4[Ag5Cl9] (I) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [AuS2CN(CH2)62]+ (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9]4– are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)–Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

Crystalline pseudopolymeric thallium(I) di-iso-pentyl dithiophosphate (Dtph), [TlS2P(O-iso-С5H11)2] (I), is synthesized and characterized in detail by single-crystal XRD (CIF file CCDC no. 2296421), simultaneous thermal analysis (STA), multinuclear (1H, 13C, 31P) NMR, and IR spectroscopy. Nonequivalent molecules of two types containing Tl(1) and Tl(2) atoms (hereinafter molecules А and В , respectively) are involved (1 : 1) in the formation of the structure of compound I. In both molecules, the S,S ′-anisobidentate coordination of the Dtph ligands (Tl–S bond lengths 3.006–3.092 Å) results in the formation of small-size four-membered metallocycles [TlS2P] (a ‘butterfly’ conformation) with significantly averaged P–S bond lengths (1.966–1.985 Å). Molecules A and B are structurally ordered upon the construction of supramolecular chains of two types (⋅⋅⋅A⋅⋅⋅A⋅⋅⋅A⋅⋅⋅)n and (⋅⋅⋅B⋅⋅⋅B⋅⋅⋅B⋅⋅⋅)n with oppositely directed structural units combined by paired secondary Tl⋅⋅⋅S and Tl⋅⋅⋅O interactions alternating over the chain length. In turn, paired secondary (but weaker) Tl⋅⋅⋅S interactions occur between molecules A and B belonging to two neighboring pseudopolymeric chains. The multiplicity of these interactions provides the formation of double supramolecular ribbons. The thermal behavior of compound I is studied by the STA technique under an argon atmosphere. Thallium(I) tetrathiophosphate Tl3PS4 is identified as the only end product of the thermolysis of compound I. Electron probe microanalysis (EPMA) and scanning electron microscopy (SEM) are used to study the residual substance.

Pseudo-polymeric double complexes of [Au{S2CN(C4H9)2}2][AgCl2] 2 CN(C 4 H 9 ) 2 } 2 ][AgCl 2 ] (1) 1 ) and [Au{S2CN(CH2)6}2]3[AgCl2] 2 CN(CH 2 ) 6 } 2 ] 3 [AgCl 2 ] [Ag 0.59 Au 0.41 Cl 2 ] 2 have been obtained and chemically identified using solution (1H, 1 H, 13 C{ 1 H}) NMR and FT-IR spectroscopy. According to XRD analysis, it was established that both of the above crystalline compounds form complicated supramolecular architectures. Self-assembly and structural stabilization of these supramolecular formations are achieved due to numerous secondary interactions: Ag center dot center dot center dot S, Cl center dot center dot center dot S (in 1 , 2 ) and Au center dot center dot center dot Cl, Au center dot center dot center dot S (in 2 ), which arose between the ionic structural units of the complexes. The combined manifestation of these interionic secondary interactions leads to the construction of two types of pseudo-polymeric chains of (center dot center dot center dot[Au (S2CNBu2)2]center dot center dot center dot[AgCl2]center dot center dot center dot)n 2 CNBu 2 ) 2 ]center dot center dot center dot[AgCl 2 ]center dot center dot center dot) n (1) 1 ) and (center dot center dot center dot[Au2(S2CNHm)4]center dot center dot center dot 2 (S 2 CNHm) 4 ]center dot center dot center dot [AgCl2]center dot center dot center dot)n 2 ]center dot center dot center dot) n (2). 2 ). To study the thermal behaviour of the prepared compounds, the simultaneous thermal analysis (STA) technique was used, which allowed us to determine the conditions for the quantitative recovery of bound metals. Moreover, a high in vitro biological activity for each of the prepared gold(III)-silver(I) compounds against the non-pathogenic strain Mycolicibacterium smegmatis was experimentally revealed.

New crystalline pseudo-polymer complex [Au{S2CN(CH2)(6)}(2)](4)[Ag5Cl9] (I) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [Au{S2CN(CH2)(6)}(2)](+) (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9](4-) are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions ClS and AgS, hydrogen bonds C-HCl, and anagostic interactions C-HAg, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)-Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

New crystalline pseudo-polymer complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] (I) was prepared by inding gold(III) with silver(I) dithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I is isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations [Au{S2CN(CH2)6}2]+ (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9]4– are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag leading to the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)—Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

Bismuth(III) hexamethylenedithiocarbamate (HmDtc) [Bi 2 {S 2 CN(CH 2 ) 6 } 6 ] ( I ) and its solvated with dimethyl sulfoxide form [Bi 2 (S 2 CNHm) 6 ]⋅2(CH 3 ) 2 SO ( II ) have been obtained. The crystal structure of compound I shows an unusual alternation of two unsymmetrical isomeric pseudo-binuclear [Bi 1/1B (HmDtc) 3 ···Bi 1A/1C (HmDtc) 3 ] molecules, each of which involves two non-equivalent mononuclear moieties combined by secondary Bi···S bonds. The solvation of complex I leads to the structural unification of isomeric [Bi(HmDtc) 3 ] molecules followed by their self-organization into centrosymmetric pseudo-dimers in the structure of compound II . All HmDtc ligands coordinate in S , S '-anisobidentate mode to form four isomeric (in I ) or structurally unique [Bi(HmDtc) 3 ] molecules (in II ), whose distorted polyhedra can be approximated by pentagonal pyramid or octahedron. Solvating DMSO molecules are retained in the structure II by C–H···O hydrogen bonds. The analysis of energy dispersive X-ray spectra allowed one to identify the residual matter obtained by thermolysis of the complexes as Bi 2 S 3 with admixture of Bi 0 .

Heteroleptic compounds of bismuth(III) adopting a new binuclear structural type: hexamethylenedithiocarbamato(HmDtc)-chloride of [Bi 2 (S 2 CNHm) 4 (μ 2 -Cl) 2 ] ( I ) and its solvated form [Bi 2 (S 2 CNHm) 4 (μ 2 -Cl) 2 ]·2CH 2 Cl 2 ( II ) have been isolated and studied by X-ray diffraction, IR spectroscopy, and simultaneous thermal analysis. Despite the identical chemical composition, the structure of binuclear molecules in I and II differs significantly. In the first case, the noncentrosymmetric molecule includes two nonequivalent moieties of [Bi(S 2 CNHm) 2 Cl], which are combined by μ 2 -Cl ligands to form the [Bi–(μ 2 -Cl) 2 –Bi] metallocycle in the butterfly conformation: Bi(1)–Bi(2) 4.0785(5) Å, Cl(1)–Cl(2) 3.936(2) Å. On the contrary, in the solvated form II , the complex is centrosymmetric and four-membered [Bi 2 Cl 2 ] ring is stabilized in a rhombic configuration: Bi(1)–Bi(1) a 3.9592(9) Å and Cl(1)–Cl(1) a 4.540(4) Å. According to the microprobe method, the main residual substance after the thermolysis of the complexes is microcrystalline Bi 2 S 3 with inclusions of metallic bismuth particles.

The reaction of binuclear zinc dipropyldithiocarbamate [Zn 2 {S 2 CN(C 3 H 7 ) 2 } 4 ] with an AuCl 3 /2 М HCl solution is studied. The double ionic complex [Au{S 2 CN(C 3 H 7 ) 2 } 2 ] 2 [ZnCl 4 ] ( I ) is identified as the main species of gold(III) binding in the heterogeneous system under study and is characterized by 13 С and 15 N CP-MAS NMR spectroscopy. Single crystals of heterovalent compound [Au{S 2 CN(C 3 H 7 ) 2 } 2 ] 2 [AuCl 4 ][AuCl 2 ] ( II ) are sampled as a by-product. The crystal and supramolecular structures of complexes I and II are determined by the direct XRD method (CIF files CCDC nos. 2159171 and 2159170, respectively). The self-organization of the complex pseudopolymeric structures of compounds I and II are shown to be due to the binding of ionic structural units by secondary nonvalent interactions Au⋅⋅⋅S and S⋅⋅⋅Cl and hydrogen bonds C–H⋅⋅⋅Cl. The thermal behavior of the complexes is studied by simultaneous thermal analysis (STA), and the quantitative regeneration of bound gold ( I and II ) with the partial transformation of released ZnCl 2 to ZnS ( I ) is found.

Bismuth(III) hexamethylenedithiocarbamate (HmDtc) [Bi2S2CN(CH2)66] (I) and its solvated with dimethyl sulfoxide form [Bi2(S2CNHm)6]⋅2(CH3)2SO (II) have been obtained. The crystal structure of compound I shows an unusual alternation of two unsymmetrical isomeric pseudo-binuclear [Bi1/1B(HmDtc)3···Bi1A/1C(HmDtc)3] molecules, each of which involves two non-equivalent mononuclear moieties combined by secondary Bi···S bonds. The solvation of complex I leads to the structural unification of isomeric [Bi(HmDtc)3] molecules followed by their self-organization into centrosymmetric pseudo-dimers in the structure of compound II. All HmDtc ligands coordinate in S,S'-anisobidentate mode to form four isomeric (in I) or structurally unique [Bi(HmDtc)3] molecules (in II), whose distorted polyhedra can be approximated by pentagonal pyramid or octahedron. Solvating DMSO molecules are retained in the structure II by C–H···O hydrogen bonds. The analysis of energy dispersive X-ray spectra allowed one to identify the residual matter obtained by thermolysis of the complexes as Bi2S3 with admixture of Bi0.

Heteroleptic compounds of bismuth(III) adopting a new binuclear structural type: hexamethylenedithiocarbamato(HmDtc)-chloride of [Bi2(S2CNHm)4(μ2-Cl)2] (I) and its solvated form [Bi2(S2CNHm)4(μ2-Cl)2]·2CH2Cl2 (II) have been isolated and studied by X-ray diffraction, IR spectroscopy, and simultaneous thermal analysis. Despite the identical chemical composition, the structure of binuclear molecules in I and II differs significantly. In the first case, the noncentrosymmetric molecule includes two nonequivalent moieties of [Bi(S2CNHm)2Cl], which are combined by μ2-Cl ligands to form the [Bi–(μ2-Cl)2–Bi] metallocycle in the butterfly conformation: Bi(1)–Bi(2) 4.0785(5) Å, Cl(1)–Cl(2) 3.936(2) Å. On the contrary, in the solvated form II, the complex is centrosymmetric and four-membered [Bi2Cl2] ring is stabilized in a rhombic configuration: Bi(1)–Bi(1)a 3.9592(9) Å and Cl(1)–Cl(1)a 4.540(4) Å. According to the microprobe method, the main residual substance after the thermolysis of the complexes is microcrystalline Bi2S3 with inclusions of metallic bismuth particles.

The capability of thallium(I) alkylenedithiocarbamates to bind gold(III) from solutions in 2 M HCl was studied. Double complexes [AuS2CN(CH2)52][TlCl4] and [AuS2CN(CH2)62][TlCl4] were preparatively isolated as individual forms of gold(III) fixation to the solid phase. In the crystalline state, the ionic structural units of the complexes are combined together by the secondary Au···S, Tl···S, and S···Cl bonds that results in complicated supramolecular architectures. Thermal behavior of the compounds was studied using the simultaneous thermal analysis technique; reduced elemental gold and thallium(I) chloride were identified as the final thermolysis products.

Liposome surface potential effect on cellular uptake and cytotoxicity is evaluated using liposomes, modified with cationic lipid DOTAP, a series of cationic gemini surfactants with two carbamate fragments, and an amphiphilic peptide SSRGD. The surfactants used are novel representatives of the gemini family with improved self-assembling activity coupled with potential biodegradable properties and displayed increasing antibacterial activity and cytotoxicity with the shortening of hydrophobic alkyl tails. The longest alkyl tail surfactant, 14-6-14(Et), was the most biocompatible of the series, which was chosen for liposome modification. Prepared liposomes of various compositions are characterized from morphological and physicochemical standpoints in order to optimize their biocompatibility and stability. The carbamate gemini surfactants were also twice as effective at providing positive charge to liposomes and less toxic compared to DOTAP. On their own, carbamate surfactants were able to increase cellular uptake of liposomes by 190%. The mixed composition of 14-6-14(Et) surfactant and SSRGD amphiphilic peptide was the most readily absorbed formulation among different tested neutral, cationic and RGD-modified liposomes. The comparison between the cellular uptake promotion is conducted as to what is the most selective and efficient approach to enhance lipid nanoparticle uptake by cancerous cells.

Pseudobinuclear, [Bi(S2CNiPr2)3]2 (I), and 1D pseudopolymeric, [Bi(S2CNiPr2)2][Bi(S2CNiPr2)Cl3] (II), bismuth(III) complexes have been synthesized and structurally characterized. Secondary Bi⋅⋅⋅S, Bi⋅⋅⋅Cl, and S⋅⋅⋅Cl bonds combine mononuclear structural units of the complexes, playing a key role in self-assembly of their supramolecular structures. The thermal behavior of the compounds has been studied by simultaneous thermal analysis under an argon atmosphere. It has been determined by energy dispersive X-ray microanalysis and scanning electron microscopy that the residual substances after thermolysis of I/II are microcrystalline Bi2S3/Bi2S3, BiCl3.

The reaction of a solution of H[AuCl4] with 1,10-phenanthroline (Phen) in acetonitrile gave the complex (H2Phen)[AuCl4]Cl (I). According to X-ray diffraction data (CCDC no. 2165199), Phen exists in I as an unusual doubly protonated (cationic) form (H2Phen)2+. Binding of ionic structural units ([AuCl4]–, Cl–, and (H2Phen)2+) by D–H···Cl hydrogen bonds (D = N, C) gives rise to supramolecular 2D pseudo-polymer layers. The biological activity of I was measured for human ovarian carcinoma cells (SKOV3). Using MTT assay results, the half-maximal inhibitory concentration was calculated, demonstrating high selectivity of I to cancer cells in combination with low toxicity towards normal fibroblasts.

An ionic Au(III)-Zn(II) dithiocarbamato-chlorido compound of [H3O][Au{S2CN(CH2)5}2]3[ZnCl4]2 (1) has been synthesised by the reaction of binuclear zinc(II) pentamethylenedithiocarbamate with a H[AuCl4]/2.0 M HCl solution. The obtained complex was successfully characterised by FT-IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. There are six ionic moieties in the unit cell of 1: (i) three dithiocarbamato-gold(III) cations, one of which is structurally inequivalent to the other two; (ii) two symmetrically related tetrachloridozincate(II) anions and (iii) one hydronium cation that is disordered over four positions with equal occupancies of 0.25. The compound exhibits a rather complicated supramolecular structure, including pseudo-binuclear gold-rich [Au2(S2CNPm)4]2+ cations and {[ZnCl4]2}4– counter anions, which are stabilised by secondary Au···S and Cl···Cl interactions, respectively. In turn, the former pseudo-binuclear formations involving centrosymmetric mononuclear cations of [Au(S2CNPm)2]+ give the pseudo-polymeric cationic chains of (···[Au2(S2CNPm)4]2+···[Au(S2CNPm)2]+···)n; while the latter, pseudo-binuclear zinc(II) anions, {[ZnCl4]2}4–, as the double linkers combine the neighbouring cationic chains yielding a two-dimensional pseudo-polymeric network. The results on the biological activity of 1 in vitro against the non-pathogenic strain Mycolicibacterium smegmatis (MIC 0.05 µg/disc) and virulent strains Mycobacterium tuberculosis H37Rv (0.14–0.19 µg/mL) and CN-40 (0.11–0.14 µg/mL) indicate a high efficiency of the studied Au(III)–Zn(II) compound against mycobacteria.

The double Au(III)–Ag(I) complex crystallizing as the solvated form of [Au{S 2 CN(CH 2 ) 5 } 2 ] 2 [Ag 2 Cl 4 ]· CH 2 Cl 2 ( I ) was obtained by the reaction of silver(I) N , N -pentamethylenedithiocarbamate with a solution of Na[AuCl 4 ]/5.15 M NaCl. According to X-ray diffraction data (CIF file CCDC no. 2062810), the structural units of the compound are nonequivalent [Au{S 2 CN(CH 2 ) 5 } 2 ] + cations (noncentrosymmetric A and centrosymmetric B and C in a ratio of 2 : 1 : 1), cyclic tetrachlorodiargentate(I) anions, [Ag 2 Cl 4 ] 2– , and solvating CH 2 Cl 2 molecule. The latter is retained in the structure due to two nonequivalent C–H···Cl hydrogen bonds formed with the cyclic [Ag 2 Cl 4 ] 2– anion involving its terminal Cl(1) and bridging Cl(2) chlorine atoms. The supramolecular self-organization of I is based on a system of multiple Ag···S and Cl···S secondary interactions that сombine the ionic structural units of the complex into an intricate two-dimensional pseudopolymer layer. A study of the thermal behavior of I by simultaneous thermal analysis established the conditions for quantitative reduction of bound gold(III) and silver(I). The studied Au(III)–Ag(I) compound exhibits a high level of biological activity against the nonpathogenic M . smegmatis strain.

Chemisorption binding of gold(III) by mercury(II) N,N-diisobutyldithiocarbamate from a solution of H[AuCl4] in 2 M HCl is accompanied by a complete redistribution of ligands between the coordination spheres of metals, which leads to the formation of the [Au(S2CNBui2)2]2[Hg2Cl6] compound belonging to double complex salts. According to X-ray diffraction data, the mutual binding of ionic structural units due to non-valent secondary (Au···S and S···Cl) interactions promotes the formation of a supramolecular 2D pseudopolymer structure of the complex. Thermolysis of this complex was studied by the simultaneous thermal analysis method.