[Ag₂(C₃₃H₂₆N₂O₂)(H₂O)₂(SO₃CF₃)₂]·0.5C₆H₆:  A Luminescent Supramolecular Silver(I) Complex Based on Metal−Carbon and Metal−Heteroatom Interactions

Abstract

A novel fulvene-type bidentate ligand 1 has been synthesized by an aroylation reaction of cyclohexyl-substituted cyclopentadienyl anions. Compound 1 crystallizes in the triclinic space group P(-)1, with a = 7.0419(5) A, b = 11.9360(8) A, c = 15.6470(11) A, alpha = 85.1440(10) degrees, beta = 78.1140(10) degrees, gamma = 74.5360(10) degrees, V = 1239.76(15) A(3), and Z = 2. The coordination chemistry of 1 was investigated, and a novel Ag-containing coordination polymer (2), linked by both Ag-heteroatom and Ag-carbon interactions, has been synthesized. The coordination polymer has been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Compound 2 crystallizes in the triclinic space group P(-)1, with a = 7.1654(5) A, b = 15.7277(11) A, c = 18.8157(13) A, alpha = 73.5150(10) degrees, beta = 89.0410(10) degrees, gamma = 89.0970(10) degrees, V = 1355.19(14) A(3), and Z = 2. The solid-state structure of 2 features a one-dimensional double-chain motif. These double chains are in turn cross-linked to each other via strong interchain O-H...O hydrogen bonds, forming a novel two-dimensional network with remarkably large cavities (effective cross section of ca. 21 x 15 A) that are occupied by benzene guest molecules. Both compounds 1 and 2 are luminescent in the solid state, and a large blue-shift in the emission between the free ligand 1 and the ligand incorporated into complex 2 is observed.

Anion controlled structural variation of silver(I) coordination polymers with a new donor–π–acceptor ligand

“…Each 2D network is packed on top of another via Ag-C(arene) interactions (3.055, 3.249 Å) and C(sp 2 )-HÁ Á ÁF hydrogen bonding interactions (Table 3). The Ag-C interactions are considerably greater than the limits (2.47-2.76 Å) commonly observed in Ag(I)-aromatic complexes [14].…”

“…The Ag-C contacts (2.746, 2.871 Å) are slightly greater than the limits (2.47-2.76 Å) commonly observed in Ag(I)-aromatic complexes. Thus, the benzene ring in 3 coordinates to the Ag(I) ion with an g 2 bonding mode, which is normally observed in arene-metal complexes [14]. Table 3 6 Geometrical parameters for various noncovalent interactions found in 2 and 3.…”

Construction of a series of inorganic–organic hybrid coordination polymers based on hexamethylenetetramine and sulfonate ligands

“…So far, a number of silver complexes incorporating organic ligands have been investigated at room temperature [54][55][56][57]. In this work, the photoluminescent behaviors of the compounds 1, 2, 4-6 and free ligands were studied in the solid state at room temperature ( Fig.…”

A three-dimensional highly stable Zn(II) coordination polymer based on 1,4-benzeneditetrazolate (H2BDT): Synthesis, crystal structure, and luminescent properties

“…Therefore, the combination of metal centers and organic spacers is considered an efficient method for obtaining new types of luminescent materials for potential applications as light-emitting diodes (LEDs) [14]. To date, among the transition metal coordination polymers, those with good luminescent abilities are mostly assembled from Zn(II) or Cd(II) centers, as this two type of ions have filled, core-like d-orbitals and thus no d-d transitions are possible [15].…”