Bridged Silver(I) Complexes of the Polycyclic Aromatic Compounds Tetraphenylethylene and 1,1,4,4-Tetraphenyl-1,3-butadiene

Abstract

For the purpose of investigating the coordination behavior of the sterically congested alkenes and exploring the possibility of cofacial complexation in the polycyclic aromatic system for formation of extended polymeric networks, tetraphenylethylene (tphe) and 1,1,4,4-tetraphenyl-1,3-butadiene (tphb) have been studied with regard to their complexation with a silver(I) ion. The crystal structures of [Ag(tphe)(ClO4)(p-xylene)], [Ag2(tphe)(ClO4)2], [Ag4(tphe)(CF3SO3)4], [Ag2(tphb)(ClO4)2], and [Ag2(tphb)(CF3SO3)2], together with the metal-free ligands tphe and tphb, have been determined by single-crystal X-ray diffraction. The pi-electron-rich cleft in organic components is found to offer a potential site for complexation, which can be utilized to generate an interesting array of organometallic compounds with one- and two-dimensional frameworks.

Silver–Ethene Complexes [Ag(η2‐C2H4)n][Al(ORF)4] with n=1, 2, 3 (RF=Fluorine‐Substituted Group)

“…These compounds are complexes of [Ag][A] (e.g. : A = BF 4 , ClO 4 , SO 3 CF 3 ) with chelating ligands such as 1,5-hexadiene, [28] norbornadiene, [22] 1,4,7-cyclononatriene, [23] 1,3,5,7-cyclooctatetraene (and derivatives), [20,24,25,50,51] bullvalene, [26] tetraphenylethene, -butadiene [19] and other substituted alkenes. [17,18,21,27,52] However, these olefins are solids or liquids and, therefore, the entropic contribution to dissociation (and thus decomposition) is much smaller than that for the lightest parent olefin C 2 H 4 .…”

“…Solution NMR spectroscopy: Signals of the 1 H, 13 C, 19 F, and 27 Al NMR spectra of 1 to 5 in CD 2 Cl 2 that can be assigned to the anionic parts [A] are similar to other salts with the same anions [59] and are therefore not discussed in detail.…”

“…In contrast to the preliminary communication of this compound, [70] the present data set was re-recorded at 100 K (vs. 150 K in Ref. [19]) and angular data up to 2q = 1008 were considered. The only clear difference between the data sets are the C=C bond lengths that are significantly longer in the new measurement, that is, 132.9(2) to 133.7(2) pm (133.3 pm av.)…”

Polarized Absorption, Spontaneous and Stimulated Blue Light Emission of J‐type Tetraphenylbutadiene Monocrystals

“…The starting molecular geometry was extracted from ref. [26] followed by geometry optimization performed using the restricted Hartree-Fock Austin model 1 (AM1) method. The optical transitions were calculated with ZINDO/S, which uses theoretically based intermediate neglect of differential overlap (INDO) parameterized to reproduce UV/VIS spectroscopic transitions with a configuration interaction (CI) including all singly excited configurations, with 10 eV limit between the occupied and unoccupied orbitals.…”

“…Two of them have monoclinic crystallographic structures and have been directly observed during our study, while a triclinic polymorph is reported in the literature. [26] The unit cell of one of the monoclinic polymorphs is reported by Baba et al [27] Here, we focus on the optical properties of the other monoclinic polymorph, whose crystallographic structure, to our knowledge, is not reported in the literature. The space group of this new polymorph is P2 1 /c.…”