Piperazinium, Ethylenediammonium or 4,4′‐Bipyridinium Halocuprates(I) by Cu^II/Cu⁰ Comproportionation

Abstract

1‐Dimensional halocuprate(I) chains [(Cu2X4)2–]n (= [(CuX2)–]n, X = Cl, Br, I) have been synthesized under hydrothermal conditions through in‐situ reduction of CuIIX2 with FeIIX2 or as phase pure materials through comproportionation of CuIIX2 or CuIIO with Cu0 metal in the presence of the respective aqueous hydrogen halide HX and a templating amine. Chains of trans edge‐sharing tetrahedra are obtained with piperazinium or ethylenediammonium dications, while the 4,4′‐bipyridinium dication gave chains of cis edge‐sharing tetrahedra. Two monoprotonated piperazinium groups act as cationic ligands (Hpipz+) towards copper atoms in a molecular [Cu4(μ‐Br6)(Hpipz)2] cluster. Electrical crystal conductivities of the halocuprate [(Cu2X4)2–]n (= [(CuX2)–]n) chains (X = Cl, Br, I) are around 10–8 S·cm–1 at room temperature.

Predesigned synthesis of dinuclear to unusual hexanuclear to 1D coordination polymer of Cu(I)-halides and their and photophysical properties

“…They are very important for their semiconducting, magnetic and photochromic properties. Preparations of such compounds are affected by many factors like CuX-to-ligand ratio, flexibility and rigidity of the ligands, solvents and temperature [12,13].…”

Isolation and X-Ray Characterization of {[Phthalazinium](CuCl2)}∞: ANew Example of a Dichlorocuprate(I) Presenting aRare Staircase Chain Structure

“…However, and confirmed by an updated CCDC query, it appears that dihalocuprates(I) associated with organic cations rarely exhibit a staircase chain with Brought to you by | MIT Libraries Authenticated Download Date | 5/11/18 5:32 AM terminal halides. Recently, C. Janiak and coworkers reported such a structure for a piperazinium dibromocuprate(I) also described as being a cis edgesharing of arrangement tetrahedral [4]. To our knowledge, {[phthalazinium](CuCl 2 )} ∞ (5) constitutes the first example of a dichlorocuprate(I) presenting a staircase chain structure and thus expands the existing structural diversity of halocuprates(I).…”

“…Well-soluble in halogenated solvents, salt 3 was fully characterized by multinuclear NMR spectroscopy. In the 19 (4), was prepared in the same way using PBz 3 . Rapidly, the addition of PBz 3 to a dichloromethane solution of 2 led to the precipitation of a pale-yellow powder characterized thereafter as being 4.…”

“…Until now, such polymeric frameworks implicating terminally bound halogen ligands were rarely observed for halocuprate(I) derivatives. To our knowledge, only one example has been recently reported in the literature by C. Janiak and coworkers [4]. In addition, the formation of {[phthalazinium](CuCl 2 )} ∞ from the starting salt [Cu 2 (µ-phtz) 3 …”

Synthesis, crystal structures and supramolecular architectures of square pyramidal Cu(II) complexes containing aromatic chelating N,N’-donor ligands

“…The H-bonds to a charged carboxylate group or nitrate anion can be termed "charge-assisted H-bonds", here the carboxylate or nitrate groups as hydrogen bond acceptors carry negative ionic charges. Such charge-assisted H-bonds are much stronger than hydrogen bonds between neutral atoms [60][61][62][63][64][65][66][67]. Each of the monomer is connected to each other by (O1W-H2W…O6 X (symmetry code x = −x,-y,1-z hydrogen bonds) inbetween the coordinated apical nitrate anions and coordinated water molecules (Figure 5b).…”