Synthesis of highly-soluble push–pull perylenemonoimide derivatives by regioselective peri-functionalization for switchable memory applications

Abstract

A regioselective synthetic protocol is developed via tetrabromination of perylenemonoimide (PMI) which leads to a series of PMI derivatives.

Perylene Monoimide as a Versatile Fluoroprobe: The Past, Present, and Future

“…Inspired by this strategy shown by them, our group also carried out S/Se annulation reaction in the peri-position of substituted-PMI and was successful in achieving good yield (as shown in Figure 12). 27 The S/Se annulated compounds exhibited drastic change of visible color along with extension of absorption characteristics due to the ICT effect. Wangʼs group reported a new PMI-coronene hybrid material by ring fusion and acquired an appreciable yield (as shown in Figure 13).…”

“…When tetra-brominated PMI 14 was treated with 4-tert-octylphenol, thiophenol and 3hydroxypyridine in presence of base, all the four bromine atoms were replaced with their corresponding nucleophiles to get 53, 54 and 56 in good to excellent yields 57%, 86% and 82% respectively (as shown in Figure 10). 27 Figure 10 Nucleophilic substitution reaction on tetra-bromo 2-ethyl-1-hexyl PMI Previous studies bring forth the conception that bromine atoms at the peri-position of PMI exhibits different reactivity than the ones at the bay-position, 33 Validating this proposition, tetrabrominated PMI 14 upon reaction with piperidine at 55 °C for 24 h gives regioselective peri-substituted PMI 55 with both the bromine atoms at bay-position remaining inactive (as shown in Figure 10 c pathway). 27…”

“…27 Figure 10 Nucleophilic substitution reaction on tetra-bromo 2-ethyl-1-hexyl PMI Previous studies bring forth the conception that bromine atoms at the peri-position of PMI exhibits different reactivity than the ones at the bay-position, 33 Validating this proposition, tetrabrominated PMI 14 upon reaction with piperidine at 55 °C for 24 h gives regioselective peri-substituted PMI 55 with both the bromine atoms at bay-position remaining inactive (as shown in Figure 10 c pathway). 27…”

“…Inspired by this strategy shown by them, our group also carried out S/Se annulation reaction in the peri-position of substituted-PMI and was successful in achieving good yield (as shown in Figure 12). 27 Figure 12 Synthesis of S/Se annulated bay-functionalized PMI compounds…”

“…26 Later, our group developed a synthetic protocol for the facile synthesis of tetra-brominated PMI with a relatively simple workup procedure. 27 In this protocol, we treated PMI 2 with 200 equivalents of bromine which affords 1,6,9,10-tetra-bromo PMI in 46% yield (as shown in Figure 5 ). Recently, Penevaʼs group reported a synthetic procedure in which they have reported the synthesis of 1,6,9,10- and 1,7,9,10-tetrabromoperylene-3,4-dibutylester in three steps from perylene 3,4,9,10-dianhydride ( 4 ).…”