Synthesis, structures, and luminescence properties of ternary supramolecular hydrogen‐bonded complexes involving [(o‐C₆F₄)Hg]₃, carbazole, and a Lewis base

Abstract

The interaction of trimeric perfluoroortho-phenylene mercury (1) with carbazole in dichloromethane3 and 4 have been characterized by elemental analysis, IR spectroscopy, and luminescence spectroscopy. The crystal structures of 3 and 4 have also been determined. Both adducts have extended structures that exhibit supramolecular binary stacks, where molecules of 1 and the carbazole-Lewis base complex alternate. Short Hg-C contacts involving molecules of 1 and carbazole indicate the presence of secondary Hg-π interactions. In addition, adducts 3 and 4 display hydrogen-bonding interactions between the acidic N H moiety of carbazole and the heteroatom of the Lewis base. The presence of this hydrogen bond is also confirmed by IR spectroscopy, which shows that the ν N−H of 3 and 4 is lower than that of 2. The luminescence spectra of these adducts correspond to the phosphorescence of carbazole, which is induced by the mercury heavy atom effect. In the case of 3 and 4, additional low-energy bands are observed at 578 and 567

Parallel and Perpendicular Packing in Mixed-Stack Cocrystals of Trimeric Perfluoro-ortho-phenylene Mercury and Benzo[1,2-b:6,5-b′]dithiophene-4,5-dione Derivatives

“…The single crystal structures of these BDDO derivatives, with the exception of BDDO and Th-BDDO, were recently reported. 23 As observed in our previous experiments with TPPM, 13 finding the best conditions for the growth of the crystals suitable for single-crystal X-ray studies required tuning the solvent and molecular ratio.…”

“…In addition to mixed-stack donor−acceptor cocrystals formed from purely organic materials, the possibility also exists to develop mixed cocrystals from a combination of organic and organometallic species. For instance, trimeric perfluoro-ophenylene mercury (TPPM) (Figure 1) is a cyclic organometallic macrocycle with strong π-electron accepting properties (the reduction potential is −1.70 V vs Cp 2 Fe 0/+ in 0.1 M tetrabutylammonium hexafluorophosphate in dichloromethane 9 ) and oxo-and thiophilicity, 9,10 that has been shown to 15.6197 (13) 9.834 (2) 10.6085 (18) 10.8919 (13) 13.839 (3) 13.299 (3) b, Å 15.371 (5) 15.6197 (13) 11.555 (3) 10.9943 (19) 11.0066 (13) 14.551(3) form mixed-stack complexes with a variety of planar aromatic moleculese.g., dithieno[3,2-b:2′,3′-d]thiophene, 9 azulene, 11 tetrathiafulvalene (TTF), 12 carbazole, 13 N-methylindole, 14 Nmethylcarbazole, 15 fluorene, 16 and nonplanar aromaticse.g., corannulene, 17 and bicorannulenyl. 18 In these cocrystals, the TPPM forms mixed stacks with the organic moieties in a 1:1 ratio, with solvent molecules remaining in some instances.…”

Lewis Acidic Behavior of Fluorinated Organomercurials

“…The trinuclear mercury derivative 7 also complexes carbazole to form a binary adduct whose structure has not been elucidated . Interestingly, when 7 and carbazole are combined in the presence of a Lewis base such as THF or NEt 3 , the ternary adducts [ 7 ·(C 12 H 8 NH·THF)] and [ 7 ·(C 12 H 8 NH·NEt 3 )] (Figure ), respectively, can be isolated . In these adducts, the carabazole is hydrogen bonded to the Lewis base.…”

Structural Diversity in the Complexes of Trimeric Perfluoro-o-phenylene Mercury with Tetrathia- and Tetramethyltetraselenafulvalene

“…Since I possesses extremely strong electron acceptor properties primarily oxoand thiophilicity, 8 this rationalizes its application as an acceptor component of CT materials. The examples of complexes between I and different planar molecules such as azulene, 9 TTF, 10 and carbazole, 11 or nonplanar molecules such as corannulene 12 and bycorannulenyl 13 were reported. The complexes of I with TTF and TCNQ were first reported by Haneline and Gabbaï.…”

“…Since I possesses extremely strong electron acceptor properties primarily oxoand thiophilicity, 8 this rationalizes its application as an acceptor component of CT materials. The examples of complexes between I and different planar molecules such as azulene, 9 TTF, 10 and carbazole, 11 or nonplanar molecules such as corannulene 12 and bycorannulenyl 13 were reported. The complexes of I with TTF and TCNQ were first reported by Haneline and Gabbai ̈.10 Having experience in the chemistry of this metallocycle 14 and encouraged by that research, we aimed to reproduce the system I−TTF with an emphasis on possible different stoichiometry and polymorphic modifications in that system.…”