A Phthalocyanine Clathrate of Cubic Symmetry Containing Interconnected Solvent‐Filled Voids of Nanometer Dimensions

Abstract

Riesenräume! Ein auf Zink[octa(2,6‐diisopropylphenoxy)phthalocyanin] basierendes Clathrat enthält in seiner Struktur solvensgefüllte ungewöhnlich große Hohlräume (>8 nm3; die Packungsanordnung ist gezeigt). Jeder Nanohohlraum ist von einer kubischen Anordnung aus 6 Phthalocyaninmolekülen umschlossen und enthält 18 Wassermoleküle sowie geschätzte 65 Acetonmoleküle, die ohne Ordnungsverlust durch Methanol‐ oder Wassermoleküle ersetzt werden können.

Activation of Water at the Active‐Site Cavity of Zinc Phthalocyanine with Tris(pentafluorophenyl)borane

“…We changed poor solvent from acetone to n ‐hexane for the crystal growth of 1 with TPFB. Large crystals with a cubic morphology were obtained by the crystallization from a CHCl 3 solution of 1 by diffusing n ‐hexane, and the molecular packing arrangement of 1 in the single crystal [ Pn 3 n space group with 12 molecules of 1 in the unit cell ( a = 3.76 nm)] agreed with the reported structure . The presence of an axial O atom coordinated with the central Zn in the cone‐shaped phthalocyanine core of 1 was also confirmed (Figure S3).…”

“…ZnPcs have been widely studied as photosensitizers for the photochemical production of 1 Δ g O 2 from O 2 as well as for the dye‐sensitized solar cells;, however, there have been no reports on the reactivity of water molecules bounded to the central Zn 2+ in ZnPcs so far. The axial coordination of donor solvents such as acetone and water was confirmed by the single‐crystal X‐ray structural characterization of two ZnPcs having bulky peripheral substituents , . Bench et al reported the stable ligation of two acetone molecules with Zn 2+ in ZnPc bearing bulky perfluoro(isopropyl) units at the peripheral positions of the phthalocyanine ring .…”

“…Bench et al reported the stable ligation of two acetone molecules with Zn 2+ in ZnPc bearing bulky perfluoro(isopropyl) units at the peripheral positions of the phthalocyanine ring . McKeown et al succeeded in preparing crystalline nanoporous materials composed of steric‐crowded zinc 2,3,9,10,16,17,23,24‐octa(2,6‐diisopropylphenoxy)phthalocyanine 1 with the axial water molecules . The introduction of bulky substituents around these ZnPcs could prevent the formation of densely packed cofacial aggregates among ZnPcs and create nanoscopic cavities above and below the phthalocyanine plane.…”

“…To obtain the direct structural information on the complex of 1 with TPFB, we conducted a single‐crystal X‐ray structural analysis. McKeown et al succeeded in obtaining large cubic crystals of 1 through a slow crystallization with the diffusion of acetone into a CHCl 3 solution of 1 . However, the UV/Vis absorption spectrum of 1 with TPFB returned to that of only 1 during the diffusion of acetone, suggesting the dissociation of complex by acetone.…”

Molecular Design Rule of Phthalocyanine Dyes for Highly Efficient Near‐IR Performance in Dye‐Sensitized Solar Cells

“…Thus, the bulky substituents around the ZnPc ring were changed from 2,6‐diphenyl‐4‐methoxyphenoxy units to 2,6‐diisopropylphenoxy units in order to increase the adsorption density. Symmetrical ZnPc decorated with 2,6‐isopropylphenoxy units prevented π–π stacking of the ZnPcs within the crystals in the cubic morphology reported by McKeown et al 18. The molecular model of PcS18 reveals a small amount of steric crowding around the ZnPc ring compared to PcS17 (Figure 3), and reducing the size of peripheral substituents may lead to close packing of dyes on the TiO 2 surface.…”