Discrete Polymetallic Arrangements of Ag^I and Cu^I Ions Based on Multiple Bridging Phosphane Ligands and π–π Interactions

Abstract

A simple and straightforward approach to new polymetallic AgI and CuI supramolecules is presented. The reaction of N,P,N,P,N ligand 2 with AgI ions affords a trimetallic complex bearing a triangular Ag3 core; metallophilic interactions are stabilized by ligands that display a multiple bridging coordination mode as 10‐electron donors. Heteroleptic polymetallic AgI and CuI complexes based on ligand 2 and the 1,12‐diazaperylene (dape) ligand are obtained by an alternative molecular organization of the polymetallic arrays compared to that in homoleptic complexes of ligand 2.

Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds: Synthetic Routes, Properties, and Applications

“…Electrophilic Condensations. peri-Annulations based on Friedel−Crafts alkylation or acylation are highly useful in the synthesis of six-membered rings (Schemes 56, 70,72,75,82,97,107,125,127,134,137,143,144,179,202,217,218,220,224,225,226,241), but are also applicable for closing five-membered (Scheme 50) and seven-membered rings (Schemes 12, 187), as well as macrocycles (notably porphyrin analogues). In alkylations, the direct cyclization product typically requires an aromatization step, such as dehydrogenation (e.g., in pyrrole−aldehyde condensations, section 7), dehydration (32.6, 88.3,8), or reductive dehydroxylation (37.2; Scheme 89), whereas acylations may lead to the aromatic product via spontaneous tautomerization (e.g., 36.8).…”

“…For sterically encumbered dap derivatives ( 32.2b – d , R = Me, Et, i -Pr), pseudotetrahedral [Cu­(dap) 2 ] + complexes were reported by Holdt et al in 2009, and their stability was subsequently explored in the gas phase using ESI mass spectrometry . Polynuclear Cu I and Ag I complexes containing dap and bridging phosphane ligands, exhibiting extended π-stacking in the solid state, were synthesized by Scheer, Lescop, et al…”

“…139 For sterically encumbered dap derivatives (32.2b−d, R = Me, Et, i-Pr), pseudotetrahedral [Cu(dap) 2 ] + complexes were reported by Holdt et al in 2009, 141 and their stability was subsequently explored in the gas phase using ESI mass spectrometry. 142 Polynuclear Cu I and Ag I complexes containing dap and bridging phosphane ligands, exhibiting extended πstacking in the solid state, were synthesized by Scheer, Lescop, et al 143 The purple-red bisacridine 32.6, containing the 3,9diazaperylene motif, was prepared in 1980 by cyclodehydration of the diaminoanthraquinone derivative 32.5. 144 This strategy, first employed in 1945 by Cook and Waddington, 146 was later used by Gibson and co-workers, 144 and more recently by Bock et al, who additionally prepared the extended tetraaza derivative 32.7.…”

The Self‐Assembly of AgI‐Containing Heterobimetallic Complexes with a Discriminatory N,P‐Based Heteroditopic Ligand

“…The distance between the Ag I ions is 2.8086(8) Å, close enough to indicate a possible argentophilic interaction,, though it must be noted that the positioning of the Ag I ions in 2 appears to be directed by the L1 ligands and not the other way around. Additionally, Ag1 and Ag2 are positioned closely to each other's P donors such that they resemble a σ 3 ,λ 3 ‐P bridging binding mode . However, the Ag1–P1 and Ag2–P2 distances of 3.026(3) and 3.111(3) Å, respectively, are too long to be considered genuine Ag–P bonds.…”

The crystal structure of 1,12-diazaperylene, C18H10N2

“…The complex formation of dap with transition metal ions (Fe, Co, Ni, Cu, Zn, Ru, Os, Re, Pd, Pt, Ag, Cd) in the gas phase has been studied by electrospray ionization mass spectrometry [16,17]. Heteroleptic polymetallic Ag(I) and Cu(I) complexes were obtained and a multidentate ligand containing a large N,P,N,P,N core yielding interesting structures with π-π stacked columns or discrete sixfold stacks [18]. The title compound is closely related to 1,1′bisisoquinoline.…”