Supramolecular Isomerism in a Cadmium Bis(<i>N</i>‑Hydroxyethyl, <i>N</i>‑isopropyldithiocarbamate) Compound: Physiochemical Characterization of Ball (<i>n</i> = 2) and Chain (<i>n</i> = ∞) Forms of {Cd[S₂CN(iPr)CH₂CH₂OH]₂·solvent}_<i>n</i>

Needles of [{Cd­[S₂CN­(iPr)­CH₂CH₂OH]₂}₃·MeCN]_∞ (<b>2</b>) were harvested from a dry acetonitrile solution of Cd­[S₂CN­(iPr)­CH₂CH₂OH]₂ after one or two days and proved to be a coordination polymer in which all dithiocarbamate ligands are μ₂,κ²-tridentate, bridging two cadmium atoms and simultaneously chelating one of these. If the same solution was allowed to stand for at least several days, <b>2</b> is replaced by blocks comprising a supramolecular isomer of <b>2</b>, dimeric <b>1</b>, with formula {Cd­[S₂CN­(iPr)­CH₂CH₂OH]₂}₂·2H₂O·2MeCN, and two ligands coordinating μ₂,κ² as in <b>2</b> and the other two purely κ²-chelating. The time dependency correlates with the pivotal role of water in driving the conversion of “chain” <b>2</b> to “ball” <b>1</b>; crystals of <b>2</b> could not be isolated from “wet” acetonitrile. When each of <b>1</b> and <b>2</b> are dissolved in solution, they exhibit comparable spectroscopic attributes (¹H, ¹³C, and ¹¹³Cd NMR and UV/vis), indicating the solution structures are the same. Both <b>1</b> and <b>2</b> are luminescent in the solid state with <b>1</b> being significantly brighter than <b>2</b>. Greenockite CdS nanoparticles are generated by the thermal decomposition of both <b>1</b> and <b>2</b>

New Multi-Ferrocenyl- and Multi-Ferricenyl- Materials via Coordination-Driven Self-Assembly and via Charge-Driven Electro-Crystallization

Three new tetra-ferrocenylethynylpyridinyl copper complexes, L₄(CuI)₄ (<b>3</b>), L₄(CuBr)₂ (<b>4</b>), and L₄(CuCl)₂ (<b>5</b>) have been prepared from the reaction of ferrocenyl­ethynyl­pyridine (L)­(<b>2</b>) with copper halides CuX (with X = I^–, Br^–, Cl^–).The ligand <b>2</b> and the complexes <b>3</b>–<b>5</b> have been fully characterized by spectroscopic methods. The structures of <b>2</b>–<b>4</b> have been confirmed by single-crystal X-ray crystallography. <b>2</b> forms a dimer in the crystalline-state through C–H··N hydrogen bonds. <b>4</b> and <b>5</b> are dimers and <b>3</b> a tetramer, in all cases linked through Cu–X··Cu bridging interactions. Cyclic voltammetry in dichloroethane showed chemically reversible multiferrocenyl oxidation signals with evidence for product electro-crystallization. The oxidation products were isolated by electrodeposition onto a Pt disc electrode and investigated by scanning electron microscopy which confirmed the spontaneous formation of crystalline oxidation products with distinctive morphologies. Energy dispersive X-ray elemental analysis shows the presence of hexafluorophosphate (counterion) with the P:Fe ratio of 1:1, 0.5:1, and 1:1 for the electrocrystallized products <b>3</b>, <b>4</b>, and <b>5</b>, respectively, suggesting the formulas [<b>3</b>]⁴⁺(PF₆^–)₄, [<b>4</b>]²⁺(PF₆^–)₂, and [<b>5</b>]⁴⁺(PF₆^–)₄ for the electro-crystallized products