Simultaneous Arrangement of up to Three Different Molecules on the Pore Surface of a Metal–Macrocycle Framework: Cooperation and Competition

Abstract

Porous crystals are excellent materials with potential spatial functions through molecular encapsulation within the pores. Co-encapsulation of multiple different molecules further expands their usability and designability. Herein we report the simultaneous arrangement of up to three different guest molecules, TTF (tetrathiafulvalene), ferrocene, and fluorene, on the pore surfaces of a porous crystalline metal-macrocycle framework (MMF). The position and orientation of adsorbed molecules arranged in the pore were determined by single-crystal X-ray diffraction analysis. The anchoring effect of hydrogen bonds between the hydroxy groups of the guest molecules and inter-guest cooperation and competition are significant factors in the adsorption behaviors of the guest molecules. This finding would serve as a design basis of multicomponent functionalized nanospaces for elaborate reactions that are realized in enzymes.

Rational synthesis of benzimidazole[3]arenes by CuII-catalyzed post-macrocyclization transformation

“…A key step in the synthesis of syn - 2 and anti - 3 is post-macrocyclization transformation of macrocyclic tris( o -phenylenediamine) ( 1 ), which can be easily prepared from o -phenylenediamine and terephthalaldehyde in two steps of macrocyclization and hydrogenation. 8 a As in our previous report, 8 macrocycle 1 reacted with Pd II ions to form a trinuclear Pd II -macrocycle. However, we found that a reaction with Cu II ions produced not trinuclear Cu II -macrocycles of 1 , but two isomeric syn - and anti -benzimidazole[3]arenes ( syn - 2 and anti - 3 ) through a Cu II -catalyzed transformation reaction ( Fig.…”

Trinuclear Cage‐Like ZnII Macrocyclic Complexes: Enantiomeric Recognition and Gas Adsorption Properties

“…[8][9][10] As imilar [3+ +3] macrocycle derived from 1,2-diaminobenzene has been used to obtain metal-macrocyclef rameworks with enantiomeric pairs of guest binding pockets. [11] We have recently shown that the triphenolic [3+ +3] Schiff-base macrocycle derived from trans-1,2-diaminocyclohexane,H 3 1,o ri ts enantiomer,H 3 2,f orm trinuclear Zn II complexes.I nt hesec ompounds, two deprotonated macrocyclic units are connected by metal ions to form the cage-like molecule [Zn 3 1 2 ]w ith the interior occupiedb ys olvent molecules( Scheme 1). [8] In that respect, [Zn 3 1 2 ]r esembles larger metal-seamed nanocapsules based on two pyrogallol [4]arenes connected by Zn II ions.…”

Mechanistic Studies on Photoinduced Catalytic Olefin Migration Reactions at the Pd(II) Centers of a Porous Crystal, Metal‐Macrocycle Framework

“…[25,26] This porous crystal has one-dimensional channels with a 1.4 nm × 1.9 nm dimension that is equipped with molecular binding sites. This has been applied to site-or diastereo-selective arrangement of guest molecules [27,28] and to size-specific reactions catalyzed by an acid catalyst immobilized on the channel surface. [29] We also found a preferential photoreaction in MMF, where the photoinduced intramolecular cycloaddition of a 1,6-diene was completely suppressed and instead olefin migration reaction took place by photoirradiation.…”