Molecular Switching: A Fully Reversible, Optically Active Photochemical Switch Based on a Tetraethynylethene‐1,1′‐Binaphthalene Hybrid System

Abstract

Dedicated to Prof. Albert Eschenmoser on the occasion of his 75th birthdayThe synthesis, characterization, and physical properties of a novel, fully reversible, light-driven molecular switch, (R,R)-1/(R,R)-2, based on a tetraethynylethene-1,1'-binaphthalene hybrid system are presented. trans-Configured (R,R)-1 was synthesized in 57% yield by Stille cross-coupling between stannylated tetraethynylethene 3 and 3-iodo-1,1'-binaphthalene derivative (R)-4 (cf. Scheme 2). The cis-isomer (R,R)-2 was prepared from (R,R)-1 by photoisomerization. X-Ray crystal-structure analyses were obtained for both cisand trans-forms of the photoswitch ( Figs. 1 and 2). In the crystalline state, molecules of the cis-isomer (R,R)-2 exhibit intramolecular edge-to-face (CÀH´´´p) interactions between naphthalene rings of the two 1,1-binaphthalene moieties (Fig. 3). The switching properties were investigated by electronic absorption spectroscopy (Table and Fig. 4): irradiation at l 398 nm converts trans-isomer (R,R)-1 into cis-isomer (R,R)-2, whereas switching occurs in the opposite direction upon irradiation at l 323 nm. No thermal interconversion between the two isomers was observed in CH 2 Cl 2 at room temperature over a period of 2 ± 3 months, and the system possesses good resistance against photofatigue (Fig. 5). Investigations of the circular dichroism of (R,R)-1 and (R,R)-2 in CH 2 Cl 2 solution showed that the chiral binaphthalene moieties induce a weak Cotton effect in the achiral tetraethynylethene core (Fig. 6). System (R,R)-1/(R,R)-2 represents one of the rare switches allowing two-way photochemical interconversions, not perturbed by thermal-isomerization pathways.

Chiral and Achiral Charge‐Transfer Chromophores with a Dendralene‐Type Backbone by Electronically Controlled Cycloaddition/Cycloreversion Cascades

“…The synthesis of ( R )‐ 13 started from alkyne ( R )‐ 15 , which was prepared from ( R )‐1,1′‐bi(2,2′‐naphthol) [( R )‐BINOL] according to a published procedure 31,32. Oxidative Hay coupling with an excess of prop‐2‐yn‐1‐ol provided alcohol ( R )‐ 16 in 51 % yield together with buta‐1,3‐diyne ( R , R )‐ 17 (18 %, Scheme ), formed by homo‐coupling of ( R )‐ 15 .…”

Visible‐Light Photochromism of Triarylamine‐ or Ferrocene‐Bound Diethynylethenes that Switches Electronic Communication between Redox Sites and Luminescence

“…All of the compounds exhibited slight blueshifts in their π–π* and CT bands in the Z forms (Figure 4). It has been reported that ethynylethene derivatives without steric hindrance do not display such blueshifts upon E ‐to‐ Z isomerization 8c. d Figure 5 shows the optimized structures of ( E )‐ 4 and ( Z )‐ 4 .…”

Organotin Reagents in Cross‐Coupling Reactions

“…Saalfrank et al [182] allowed stannylalkynes or bis(trimethylstannyl)alkyne to react with bromoallenes to afford conjugated alkynylallenes or diastereomeric ynediallenes. Diederich et al [183] synthesized a novel light-driven fully reversible molecular switch by a cross-coupling between a stannylated tetraethynylethene and a 3-iodo-1,1 -binaphthyl derivative (Scheme 6.43).…”