Control over the Self‐Assembly Modes of Pt^II Complexes by Alkyl Chain Variation: From Slipped to Parallel π‐Stacks

Abstract

ABSTRACT:We report the self-assembly of a new family of hydrophobic, bis(pyridyl) Pt(II) complexes featuring an extended OPE-derived π-surface appended with six long (dodecyloxy (2)) or short (methoxy (3)

Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition‐Metal Compounds: A Theoretical Study

“…31 We performed tests were with the more recent semiempirical PM7 method, 32 but optimization problems for aggregates as small as dimers were encountered in the case of Pd(II) complexes, suggesting that this method may not be reliable, at least for the Pd(II) complexes investigated here. Also, dispersion-corrected PM6 was shown to be superior to PM7 concerning the description of non-covalent interaction.…”

“…For instance, replacing the methyl group of the side chains of 1 and 2 by long glycol and alkyl groups led to compounds able to form supramolecular stackings. 9,11,31 A closely related compound to 3 was reported by Strassert et al to form supramolecular nanowires exhibiting interesting photophysical properties. 26 The other compound was included in this series in order to allow for investigating the influence of the central metal on the assembling and final properties of the supramolecular stackings.…”

“…9,31 More importantly, it is evident from Fig. 4 that the ΔfG curve for 1 is on average steeper than that for 2, especially if we compare the corresponding trend lines (Fig.…”

“…15 This mechanism is widely used in studies of cooperativity of 1D stackings. 9,31 In mechanism II, an aggregate of n monomers is assembled from two smaller columns of m and x monomer units. The variation in Gibbs energy (ΔfG) associated to each mechanistic step was calculated in the usual way, e.g., ΔfG(7+1→8) = ΔfH(7+1→8) -TΔfS(7+1→8), where ΔfH(7+1→8) = ΔfH(8) -ΔfH(7) -ΔfH(1), and ΔfS(7+1→8) = ΔfS(8) -ΔfS(7) -ΔfS(1).…”

“…The supramolecular growths of aggregates of 1-3 were predicted to be exergonic (ΔfG < 0) at room temperature in vacuum and therefore the corresponding stacks are predicted to exist, which is in agreement with experimental data of similar compounds. 9,26,31 No experimental data on cooperativity was found for 4.…”