Facile Synthesis of the Shape‐Persistent 4‐Hydroxybenzaldehyde Based Macrocycles and Exploration of their Key Electronic Properties: An Experimental and DFT Approach

In the current study, a series of stabilized bis‐acetylene incorporated 4‐hydroxybenzaldehyde based macrocycles using the alkyne‐homocoupling approach were synthesized in moderate yields. A total of six newly stiff macrocycles were synthesized in a stepwise manner starting from 4‐hydroxybenzaldehyde. In the first step, base mediated propargylation was performed followed by copper mediated terminal alkyne homocoupling. The alkyne homocoupled substrate having carbonyl at both the terminals is cyclized in the final step via double imine formation reactions using substituted diamines as linker. All the newly synthesized rigid framework of the macrocycles were optimized at B3LYP/6‐31G (d,p) level of theory. Nonlinear optical behaviors of the synthesized macrocycles were explored by the DFT calculations where high values of first‐order hyperpolarizability and dipole moment were examined. In the reported study, a good agreement between experimental and theoretical parameters was observed that may play a significant contribution for the NLO applications. A series of six stabilized bis‐acetylene incorporated 4‐hydroxybenzaldehyde based macrocycles via alkyne‐homocoupling approach have been prepared in a stepwise manner i.e base mediated propargylation followed by copper mediated terminal alkyne homocoupling. The alkyne homocoupled substrates are finally cyclized via double imine formation reactions using substituted diamines as linker. The synthesized macrocycles were characterized by spectroscopic characterization such as 1H NMR, UV, IR and HRMS. Additionally, nonlinear optical behaviors of the synthesized macrocycles were explored by the DFT calculations.