Vito Lippolis

Template self-assembly of polyiodide networks

A range of metal thioether macrocyclic complexes has been used as templating agents in the preparation of extended multi-dimensional polyiodide arrays. A selection of unusual and intriguing polyiodides is described, and the role played by the size, shape and charge of the metal macrocyclic complex discussed.

Templatorganisation von Polyiodid-Netzwerken an komplexierten Metallkationen: Synthese und Kristallstruktur von [Pd2Cl2([18]anN2S4)]1.5I5(I3)2 und [K([15]anO5)2]I9

Mit den Kationen [Pd2Cl2L]2+ und [KL]+ (L[18]anN2S4, L′ = [15]anO5) als Templaten sind neuartige dreidimensionale Polyiodid-Netzwerke zuganglich. Die Metallkationen in [Pd2Cl2L]1.5I5(I3)2 sind durch paarweise Wasserstoffbruckenbindung zu unendlichen Ketten verknupft, wobei die resultierenden kationischen Polymere in Kanalen eines ausgedehnten Polyiodid-Netzwerks liegen. [KL]I9 hat ein dreidimensionales Netzwerk aus deformierten wurfelformigen Kafigen aus I9−-Ionen, deren Hohlraume durch die Metallkationen besetzt sind (Ausschnitt aus der Struktur rechts gezeigt).

catena‐Poly[[trans‐di­chloro­copper(II)]‐μ‐1,4,7,10,13,16‐hexa­thia­cyclo­octa­decane‐S1:S10]

In the title complex, [CuCl2(C12H24S6)]n, the CuCl2 unit and the ligand lie on and about inversion centres, respectively. The coordination geometry at CuII is a tetragonally elongated octahedron with the equatorial positions occupied by two chlorides, Cu—Cl 2.2786 (12) A, and two S donors, Cu—S 2.3710 (13) A. The apical positions of the octahedron are defined by two S donors at distances of 2.8261 (14) A from the metal. The macrocyclic ligand adopts a very puckered and distorted conformation. Eight of the 18 torsion angles are less than 90° and all S-donors are oriented exo to the ring.

4-Methoxyphenylphosphonic acid: Reactivity of Lawesson’s Reagent

The title compound, C(7)H(9)O(4)P, obtained as a by-product of the reaction between Lawessons reagent, (I), and CH(3)I, can be recognized as the final product of the S/O interchange reaction at the P atom of (I). Hydrogen bonds of type P-O-H.O=P link molecules into helical chains and form ten-membered hydrogen-bonded rings with the graph-set notation R(3)(2)(10). Weaker intermolecular contacts between P-O and a phenyl H atom link the chains into a three-dimensional lattice. The parent benzenephosphonic acid [Weakley (1976). Acta Cryst. B32, 2889-2890] does not adopt an analogous structure, but its arsenic analogue [Shimada (1960). Bull. Chem. Soc. Jpn, 33, 301-304] does and can be regarded as isostructural. We rationalize these three structures in terms of their significant intermolecular interactions.

1,4,8,11-Tetrakis(diiodine)-1,4,8,11-tetrathiacyclotetradecane

The title compound, C 10 H 20 S 4 .4I 2 , [14]aneS 4 .4I 2 , possesses crystallographically imposed inversion symmetry and has all four S donor atoms coordinated to diiodine molecules. The principal geometric parameters for the two inequivalent pairs of interactions are S-I 2.803 (2) and 2.880(2)A, I-I 2.7894 (8) and 2.7571(10)A, and S-I-I 177.71(5) and 172.50(4)°. Molecules are linked by S...I and I...I intermolecular contacts to form an infinite three-dimensional lattice.

Synthesis and characterisation of pendant-arm amino derivatives of 1,4,7-triazacyclononane and alkyl-bridged bis(1,4,7-triazacyclononane) macrocycles and complexation to Cu(II)

The new pentadentate and bis(pentadentate) ligands 1-methyl-4,7-bis(3-aminopropyl)-1,4,7-triazacyclononane 6 and 1,2-bis[4,7-bis(3-aminopropyl)-1,4,7-triazacyclonon-1-yl]ethane 14 have been synthesised by reaction of acrylonitrile with the corresponding macrocyclic precursors and subsequent reduction of the nitrile groups with BH3·THF. Cu(II) complexes of the two ligands having formulations [Cu(6)][BF4]2 and [Cu2(14)][PF6]4·6MeCN, respectively, have been prepared and structurally characterised. Both complexes exhibit distorted square-based pyramidal geometries about the metal centres with the two primary amino groups belonging to the pendant arms occupying basal positions [Cu–Nap 2.257(6), Cu–Neq 2.026(6)–2.074(5) A for [Cu(6)]2+, and 2.337(2) and 2.038(3)–2.085(3) A for [Cu2(14)]4+]. The binuclear complex [Cu2(14)]4+ is centrosymmetric about the ethane bridge with the two pentadentate compartments oriented away from one another to give a transoid anti-configuration with a MeCN molecule interacting with each Cu(II) centre at 2.710(4) A. Both complexes have also been characterised by electronic and EPR spectroscopy and by cyclic voltammetry, and their properties compared to those of Cu(II) complexes of analogous macrocyclic ligands having 2-methylpyridyl pendant arms.

Thioether crown complexes as templates for the assembly of extended polyiodide networks: synthesis and structures of {[M([16]aneS4)]2I}I11 (M = Pd, Pt), [Pd(cis-HO)2[14]aneS4)](I3)2, [Pd([9]aneS3)2](Ix)2 (x = 3, 5)

Abstract Pd(II) and Pt(II) complexes of [16]aneS4 and Pd(II) complexes of cis-(HO)2[14]aneS4 and [9]aneS3 have been used as templates for the self-assembly of polyiodide ions. The complexes {[M([16]aneS4)]2I}I11 (M = Pd, Pt), [Pd(cis-(HO)2[14]aneS4)](I3)2, [Pd([9]aneS3)2](Ix)2 (x = 3, 5) have been synthesized and structurally characterized. In {[M([16]aneS4)]2I}I11, the polyiodide network consists of fused 14-member polyanion rings made up of interacting “L”-shaped I5− and I− units; binuclear [([16]aneS4)M–I–M([16]aneS4)]3+ complex cations featuring a highly unusual linear and symmetric M–I–M moiety are each surrounded by one of these 14-member polyiodide rings in a belt-like fashion. The structures of [Pd(cis-(HO)2[14]aneS4)](I3)2 and [Pd([9]aneS3)2](I3)2 both feature tri-iodides as counter-anions. In [Pd(cis-(HO)2[14]aneS4)](I3)2, quite asymmetric I3− ions form sinusoidal infinite chains via head-to-tail I3−⋯I3− interactions; these chains run along the (001) direction and are stacked along the (100) direction to form highly puckered anionic layers via I⋯I weak interactions that cross-link the chains. In [Pd([9]aneS3)2](I3)2, [Pd([9]aneS3)2]2+ cations are bridged on each side by pairs of symmetric I3− ions through long-range S⋯I contacts to form discrete infinite ribbons that run parallel to the a axis. By contrast, the structure of [Pd([9]aneS3)2](I5)2 consists of highly puckered polyanionic layers featuring fused 18-member polyiodide rings made up of I5− ions. Two of these layers related by an inversion center are stacked along the b axis and interact with each other to form large cavities within which the complex cations sit. In these complex arrays the cation can be regarded as a template around which polyanion networks can be structured. The solid state FT-Raman spectra of the reported polyiodides are discussed on the basis of their crystal structures.

Macrocyclic Thioether Complexes of Palladium with Dibromoiodide Anions

The structure of bis(1,4,7-trithiacyclononane)palladium(II) bis(dibromoiodide), [Pd(C 6 H 12 S 3 ) 2 ](IBr 2 ) 2 , comprises ribbons in which neighbouring cations are linked by pairs of anions through S...Br contacts of 3.767 (5)-3.877 (5) A. In (1,4,8,11-tetrathiacyclotetradecane)palladium(II) bis(dibromoiodide), [Pd(C 10 H 20 S 4 )](IBr 2 ) 2 , Pd...I, S...Br and S...I contacts link cations and anions into an infinite three-dimensional network.

Chapter 8.2:Charge-Transfer (C.-T.) Adducts and Related Compounds

Reactions of di-halogens (I2, Br2) and inter-halogens (IBr, ICl) with organic molecules containing Group 16-donor atoms (LE; L = organic framework, E = S, Se, Te) have been the subject of renewed interest in the past few years both for their intrinsic interest and for their implications in different...

Bis(acetonitrile‐N)(1,4,8,12‐tetraazacyclopentadecane)nickel(II) Bis(triiodide) and (1,4,8,12‐Tetraazacyclopentadecane)palladium(II) Bis(triiodide)

In the first title compound, [Ni(C 2 H 3 N) 2 (C 11 H 26 N 4 )](I 3 ) 2 , the Ni II centre is coordinated octahedrally: all four N-donor atoms of the macrocyclic ligand occupy an equatorial plane and the coordination is completed by two axial acetonitrile ligands. Each N-H group forms a contact of 2.97-3.11 A to one I atom of an I 3 - anion. One of these anions participates in long I. . .I contacts of 4.008(3)A to form infinite chains of symmetry-related anions. In the second title compound, [Pd(C 11 H 26 N 4 )](I 3 ) 2 , each Pd II centre is coordinated in an equatorial plane by four N-donor atoms from the macrocyclic ligand and axially by a terminal iodine from each of two I 3 - anions at 3.525 (4) A. The same I atom forms an I...I contact of 4.094(3) A such that cations and pairs of anions alternate within one-dimensional zigzag chains.