Photoinduced Processes of Supramolecular Nanoarrays Composed of Porphyrin and Benzo[ghi]perylenetriimide Units through Triple Hydrogen Bonds with One‐Dimensional Columnar Phases

Abstract

One-dimensional supramolecular columnar phases composed of porphyrins (electron donor: D) and benzo[ghi]perylenetriimides (electron acceptor: A) through triple hydrogen bonds have been successfully constructed to perform sequential light-harvesting and electron-transfer processes. A series of benzo[ghi]peryleneimide derivatives have been synthesized to examine the substituent effects such as imide and nitrile groups on the spectroscopic and electrochemical properties. Then, formation of the 1:1 supramolecular complex between zinc porphyrin and benzo[ghi]perylenetriimide derivatives through triple hydrogen bonds was confirmed by Job's plot of (1) H NMR titration. Next, the one-dimensional supramolecular nanoarrays were successfully prepared in a mixed solvent. X-ray diffraction (XRD) measurement suggested that these nanoarrays contained one-dimensional columnar phases composed of stacked donor and acceptor layers. Finally, femtosecond transient absorption and electron spin resonance (ESR) measurements clearly indicated that photoinduced electron transfer occurred via the singlet excited states in the supramolecular columns.

Improving Electron Transport in a Double-Cable Conjugated Polymer via Parallel Perylenetriimide Design

“…The synthetic procedures of the monomers and polymer are shown in Scheme . The compounds 1 and 2 were synthesized according to the literatures. The double-cable polymer PTPDBPTI was prepared via Stille polymerization by using the catalyst Pd 2 (dba) 3 /P­( o -tolyl) 3 in toluene and purified via extraction by acetone, n -hexane, dichloromethane, and chlorobenzene (CB) in turns.…”

“…In this work, we have successfully developed a new method to solve electron-transport issues in these double-cable conjugated polymers toward efficient SCOSCs. The idea starts from selecting a new electron-deficient side unit benzo­[ghi]­perylene triimide (BPTI, Figure c). − BPTI has large aromatic skeleton with improved crystallinity compared to PBI unit, which will help to form ordered structures during competition with conjugated backbone. In addition, we speculate that this parallel structure will create more chance for the contact between different BPTI units, so that electron transport could be allowed (Figure b).…”

“…Synthesis. Compound 2 was synthesized according to the literature procedure 54. 1 H NMR (CDCl 3 , 400 MHz): δ (ppm) 10.37 (s, 2H), 9.36−9.39 (d, 2H), 9.19 (s, 2H), 8.03 (s, 1H), 5.30−5.31 (d, 2H), 2.34−2.37 (d, 4H), 1.97−1.98 (d, 4H), 1.30−1.33 (m, 24H), 0.81−0.86 (t, 12H).…”

Synthesis and self-assembly of a penta[60]fullerene bearing benzo[ghi]perylenetriimide units

“…16 Moreover a BPTI derivative has been used in supramolecular chemistry affording a 1 : 1 supramolecular complex with zinc porphyrin through hydrogen bonds and an ultrafast photo-induced electron transfer occurred between the two columns of donors and BPTI acceptors. 17 Fullerene C 60 thanks to its tridimensional structure and excellent electron accepting properties 18 has been widely used in the formation of supramolecular polymeric nano-network. In particular, the pentasubstituted fullerenes developed by Nakamura and co-workers are well suited.…”

“… 16 Moreover a BPTI derivative has been used in supramolecular chemistry affording a 1 : 1 supramolecular complex with zinc porphyrin through hydrogen bonds and an ultrafast photo-induced electron transfer occurred between the two columns of donors and BPTI acceptors. 17 …”