The stereochemistry of the copper(II) ion in the solid-state—some recent perspectives linking the Jahn–Teller effect, vibronic coupling, structure correlation analysis, structural pathways and comparative X-ray crystallography

A series of copper(II) complexes with substituted phenanthroline ligands has been synthesized and characterized electronically and structurally. The compounds that have been prepared include the mo...

Electronic and structural variation among copper(II) complexes with substituted phenanthrolines.

The crystal structures of [Cu(bipy)(3)][BPh(4)](2), 1, and [Zn(bipy)(3)][BPh(4)](2), have been determined at low temperature. 1 and 2 are closely related, but are not isostructural. Both contain a two-dimensional supramolecular construct (SC) involving a sandwich structure. 1 has a six-coordinate CuN(6) chromophore with a regular elongated octahedral stereochemistry and rhombic in-plane bond lengths. The associated tetragonality value, T, of 1 is 0.8868. 2 involves a six-coordinate octahedral chromophore. Differences between 1 and 2 relate to the tendency of copper(II) complexes to undergo a Jahn-Teller (JT) distortion. The zinc(II) cation feels solely the host site strain, whereas the copper(II) cation also involves vibronic JT type coupling. The copper polyhedron geometry is characterized by both phenomena, with the vibronic interaction dominating. Scatter plot analysis involving the tris-chelate copper(II) series suggests that neither pure Q(theta) or Q(epsilon) components or the a(2u) mode operate in isolation over the entire series. All three operate in combination with varying quantifiable contributions, leading to distortion from the regular tetragonal octahedral stereochemistry.

Structural systematics of the [Cu(chelate)3][Y]2 series. An interesting crystallographic structural insight involving vibronic coupling and the Jahn-Teller effect (JTE). The syntheses and low temperature crystal structures of tris(2,2'bipyridyl)copper(II) tetraphenylborate and tris(2,2'bipyridyl)zinc(II) tetraphenylborate.

Two novel diazamesocyclic ligands based on l,5-diazacyclooctane (DACO) and functionalized with additional pyridyl donor groups, namely 1,5-bis(2-pyridylmethyl)-1,5-diazacyclooctane (L1) and 1-(2-pyridylmethyl)-1,5-diazacyclooctane (L2), have been synthesized and characterized, as have their CuII complexes. Crystal structure analyses revealed that with Cu(ClO4)2L1 forms a five-coordinate mononuclear complex [CuIIL1Cl]ClO4 (1), whereas L2 forms a µ-Cl−-bridged dinuclear complex [CuII(L2)Cl]2(ClO4)2 (2). Furthermore, it has been found that the apical chloride anion of 1 may be easily exchanged by azide anion, forming the mononuclear complex [CuIIL1(N3)]ClO4 (3). There is a notable difference between 3 and 1 in that 3 forms a quasi-two-dimensional network through intermolecular C−H···O hydrogen bonds and π−π stacking interactions. Each CuII center in the three complexes is pentacoordinated in a distorted square-pyramidal environment and the DACO ring of each ligand adopts a boat-chair configuration in all the complexes. In the mononuclear complexes 1 and 3, the Cl− or N3− anions occupy the apical sites, whereas in the dinuclear complex 2 the two bridging Cl− anions occupy both axial positions as well as one equatorial position, leading to an intramolecular Cu···Cu separation of 3.396 A. Variable-temperature magnetic susceptibility measurements on 2 in the range 4−300 K indicate a weak intramolecular ferromagnetic coupling between adjacent CuII centers with 2J = 2.28 cm−1; the magneto-structural correlations are discussed in detail. The solution behavior of the complexes has been further studied by UV/vis and ESR techniques.

Novel Diazamesocyclic Ligands Functionalized with Pyridyl Donor Group(s) − Synthesis, Crystal Structures, and Properties of Their Copper(II) Complexes

Synthesis, crystal structure, spectroscopic and magnetic properties of doubly and triply bridged dinuclear copper(II) compounds containing di-2-pyridylamine as a ligand

The range in static stereochemistry of the cation distortion isomers of the [Cu (chelate)2Cl]+ cation, where chelate=bipy, phen or bipyam. The low temperature crystal structure (150 K) of [Cu (bipy)2Cl] [PF6]·H2O and [Cu (phen)2Cl] [BPh4]

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The range in static stereochemistry of the cation distortion isomers of the [Cu (chelate)2Cl]+ cation, where chelate=bipy, phen or bipyam. The low temperature crystal structure (150 K) of [Cu (bipy)2Cl] [PF6]·H2O and [Cu (phen)2Cl] [BPh4]