The biomimetic synthesis of marine alkaloid related pyrido- and pyrrolo[2,3,4-kl]acridines

2,11‐Dialkylated 1,12‐Diazaperylene Copper(I) Complexes: First Supramolecular Column Assemblies by π‐π Stacking between Homoleptic Tetrahedral Metal Complexes, Exhibiting Low‐Energy MLCT Transitions

“…The bis(2,11-diisopropyl-1,12-diazaperylene)copper(I) complex was also synthesized with iodide and 9,10-dihydro-9,10-dioxo-2-anthracenesulfonate as counterions, yielding the salts [Cu(dipdap) 2 [a] NaAQSO 3 = sodium 9,10-dihydro-9,10-dioxo-2-anthracenesulfonate. Selected structural data are given in Table 1 and the crystal data and collected parameters are listed in Tables S1-S2 (Supporting Information) 2 O, each copper(I) complex cation interacts with two others by π-π stacking interactions, forming an unprecedented supramolecular column structural motif running along the crystallographic c axis (Figure 1). The BF 4 -counterion is located between the columns (Figure 3).…”

“…[25] ), indicating strong complex formation. In the yellow and red visible range of the spectra of complexes [Cu(L) 2 ] + (L = dmedap, detdap, dipdap), at least three MLCT bands are found, one above 680 nm, a second one with the global MLCT maximum at about 615 nm and a third one exemplified by a shoulder at about 570 nm. The overall shape of the MLCT absorption bands is typical for comparable homoleptic bis(diimine)copper(I) complexes, for example, [Cu(dmephen) 2 ]BF 4 ( Figure 10).…”

“…[27] Although the absolute value of the global MLCT absorption maximum of [Cu(dipdap) 2 ]BF 4 (612 nm) differs slightly from the values of the other two 2,11-dialkyl-1,12-diazaperylene complexes (616 nm), its displacement with respect to the lowest-energy intraligand band is very similar, amounting to 5650 cm -1 for all three complexes. Whereas these energetic results are mainly related to the degree of π delocalization, the reduction of the molar absorption coefficient of [Cu(dipdap) 2 + complexes with L = 2,9-disubstituted phenanthroline, bulky substituents can interact with the ligand core of the opposite ligand, thereby reducing the conformational freedom of the substituents and entailing an increase in the average metal-ligand separation, which in turn results in a reduced intensity of the MLCT absorption. [28] …”

“…Dipyrido[3,2-a:2Ј,3Ј-c]phenazine [1] (dppz), eilatin [2] (eil) and 1,12-diazaperylene [3] (dap) are 1,10-phenanthrolinebased ligands with increased π surface that are called "large-surface" ligands (Scheme 1). [4] Metal complexes of "large-surface" ligands have enormous potential to form metal organic supramolecular assemblies by π-π stacking interactions in solution and in the solid state.…”

“…In the planar dichloro(dipyridophenazine)platinum(II) complex [PtCl 2 -(dppz)], both ligand-ligand π-π and platinum-platinum interactions lead to aggregation of this complex in the crystal, forming two infinite stacks. [5] The octahedral mono(eilatin) Ru II and Os II complexes [M(L-L) 2 (eil)] 2+ (M = Ru, Os; L-L = bipyridyl-type ligands) dimerize by π-π stacking between the eilatin moieties in the solid state and in solu- [ tion. [6] In all the solid-state structures, a well-defined discrete dimer is observed in which the eilatin surfaces are about 3.4 Å apart, a typical distance for systems held by π-π stacking interactions.…”