Synthesis and Density Functional Theory Studies of Azirinyl and Oxiranyl Functionalized Isoindigo and (3Z,3’Z)-3,3’-(ethane-1,2-diylidene)bis(indolin-2-one) Derivatives

Abstract

The design and synthesis of functionalized isoindigo compounds by reaction of isoindigo with (S)-glycidyl tosylate, epibromohydrin, 2-(bromomethyl)-1-(arylsulfonyl)aziridine, and 2-(bromomethyl)-1-(alkylsulfonyl)aziridine in the presence of MeONa proceed under mild conditions in moderate yields. (3Z,3’Z)-3,3’-(Ethane-1,2-diylidene)bis(1-(oxiran-2-ylmethyl)indolin-2-one), with an extended central olefin π-conjugated moiety was also reacted with methyl-oxiranes to give the corresponding N,N’-disubstituted derivative. Calculations with DFT and TD-DFT of hypothetical isoindigo-thiophene DA molecules with various electron withdrawing substituents, including aziridine, oxirane, nitrile, carbonyl, and sulfonate, indicated that the proximity and strength of the functional group have a significant effect on the HOMO, LUMO, vertical excitation energy, and oscillator strength of the π–π* transitions.

Unravelling the Effect of Complexant Number on Remarkably High Static and Dynamic Second Hyperpolarizability of Aziridine Based Diffuse Electron Systems: A Theoretical Study

“…Vibrational frequencies are calculated using the optimized structuresis found to be real for each vibrational mode. The B3LYP optimized structure of the aziridrine molecule agrees well with the experimental data available (proton affinity PA = 905.5 and gas-phase basicity = 872.5 kJ mol −1 ) [42,43] and this functional has also been widely used for optimizing nitrogen based heterocycles [44] and aziridrine based complexes [45].…”

“…This above functional has been widely used for evaluating the electronic property of diffuse electron systems. [64,10,58] The TD-DFT calculations of aziridine derivatives are also carried out using the aforementioned functional [45].The variation of static second hyperpolarizability along zzzz axis can be explained by the spectroscopic parameter using thetwo state model [65]. 24…”

The Synthesis and Theoretical Investigation of Functionalized N,N′‐Arylthioalkylisoindigo Derivatives

“…As part of our program directed toward the development of novel methods to construct isoindigo derivatives, [17,18] we previously developed a new synthesis of various N , N ′‐dialkylisoindigos using sodium methoxide as the base under mild condition [19] . The current studies started with the substituted thiourea compounds 2 as substrates as there is precedent for S ‐thiolation of bromoalkylisoindigo as these sulfur‐containing compounds are effective nucleophiles in the presence of sodium methoxide.…”