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• Self-assembly of the dithiophosphonate tectons generating supramolecular synthons via N H···S, N H···O, C H···S, C H···O, C H···π, and lp···π interactions. • Connection between molecular and supramolecular chirality in the crystalline state (chirogenesis). • NCI index analysis supports the proposition of P-stereogenic centers. • Chiral transference of the p atom to the supramolecular helical assembly. • Spontaneous resolution process to generate the homochiral crystal. The self-assembly of the dithiophosphonate tectons synthesized in this work generated novel supramolecular synthonsvia N H···S, N H···O, C H···S, C H···O, C H···π, and lp···π interactions. The reaction of the salts with chloro dithiastibocanes X(CH 2 CH 2 S) 2 SbCl (X = O , S) led to the formation of coordination compounds in which the crystal structures showed two new supramolecular synthons stabilized by C H···π and lp···π interactions. The theoretical study of the electronic density of the crystal and their synthons in the solid-state used the robust NCI index to confirm the nature of the interactions found. This study confirmed the connection between molecular and supramolecular chirality in the crystalline state. Three significant features unequivocally support the findings: the role of intramolecular interactions, the electronic density differences among diastereomers, and the nature of trans-annular bonds. The characterization of the salts: ammonium-menthoxy (4-methoxyphenyl) dithiophosphonate (1), triethylammonium-menthoxy (4-methoxyphenyl)-dithiophosphonate (2), triethylammonium-biphenyl-4‑methoxy (4-methoxyphenyl) dithiophosphonate (3), and the coordination compounds O(CH 2 CH 2 S) 2 Sb[S 2 P(biphenyl-4‑methoxy)(4-MeOC 6 H 4)] (4) and S(CH 2 CH 2 S) 2 Sb[S 2 P(biphenyl-4‑methoxy)(4-MeOC 6 H 4)] (5) was carried out by elemental analyses, IR, NMR (1H, 13C, 31P), and single-crystal X-ray diffraction analysis. [Display omitted] [ABSTRACT FROM AUTHOR]

Five metal complexes have been prepared by reacting 3- and 4-pyridineboronic acid (3- and 4-pba) with potassium tetrachloroplatinate (K2PtCl4) and hexachloroplatinic(IV) acid hydrate (H2PtCl6·aq): [4-pbaH]2[PtCl4], [3-pbaH]2[PtCl4], [4-pbaH][Pt(4-pba)Cl3], cis-[Pt(4-pba)2Cl2]·H2O, and cis-[PtIV(3-pba)2Cl4]·2H2O. All compounds have been characterized by single-crystal X-ray diffraction analysis, showing that the primary hydrogen bonding interactions of the resulting 1D, 2D, and 3D networks contain at least one of the following synthons: X-H···Cl2Pt−(X = C, N+), B(OH)2···Cl2Pt−, and B(OH)2···(HO)2B. The dimensions are enhanced further by secondary +N−H···ClPt, O−H···O, and O−H···ClPt hydrogen bonding interactions between donor and acceptor atoms located at the periphery of these synthons. Additional weak C−H···O, C−H···Cl, B···N, and π···π stacking interactions stabilize the crystal structures further. [ABSTRACT FROM AUTHOR]

• Three lanthanum(III) 2-amino-1-cyclopentene-1-carbodiothioate (ACDA) were obtained. • It is reported the first structural determinations of a rare earth ACDA complexes. • The ACDA is bonded to the lanthanum in a S,S coordination mode. • The DFT calculations for all the ACDA lanthanide complexes is in favor of the S,S mode. The synthesis and characterization of the first three La(III) 2-amino-1-cyclopentene-1-carbodithioate (ACDA) complexes is reported including two ionic complexes, [NEt 3 H][La(ACDA 4)] (1), [N(n - Bu) 4 ][La(ACDA 4 ] (2) and [La(ACDA) 3)(1,10-phenanthroline)] (3). The single-crystal X-ray structures of 1 – 3 correspond to the first known structural determination of ACDA rare earth complexes. Compounds 1 – 3 show an S,S coordination mode, and due to hydrogen bonding present in the ligands, secondary interactions were observed. DFT calculations for all the lanthanide series indicate that the ACDA ligand binds in an isobidentate fashion through low covalent M–S bonds, as evidenced by natural population analysis. Furthermore, the S,S coordination mode is overwhelmingly preferred over the N,S coordination, as demonstrated by free energy calculations from the vibrational frequency analysis. [Display omitted] [ABSTRACT FROM AUTHOR]