The [4 + 4] thermocyclization of 9‐anthraldehyde: synthesis,crystal structure,experimental and theoretical UV spectra,natural bonding orbital analysis and prediction of third‐order nonlinear optical properties

The dimer of 9‐anthraldehyde, namely heptacyclo8.6.6.6^2,9.0^3,8.0^11,16.0^17,22.0^23,28]octacosa‐3,5,7,11,13,15,17(22),18,20,23(28),24,26‐dodecaene‐1,9‐carbaldehyde, C₃₀H₂₀O₂, has been synthesized by refluxing an ethanol solution in the presence of M(ClO₄)₂ and 1,3‐diaminopropan‐2‐ol (M = Co²⁺ or Cu²⁺). Its structure has been determined by single‐crystal X‐ray diffraction, showing it to be a new polymorph, referred to as polymorph II, in the monoclinic space group P2₁/n. It is compared with the previously reported triclinic modification Ehrenberg (1968). Acta Cryst. B 24 , 1123–1125], which is referred to as polymorph I. The asymmetric unit of polymorph II contains two half molecules located on crystallographic centres, while the asymmetric unit of polymorph I includes one half molecule, also located on a crystallographic centre. Time‐dependent density functional theory (TD‐DFT) at the RB3LYP level using the 6‐31G(d,p) basis set was applied. The predicted electronic absorption spectrum is in good agreement with the experimental one. The analysis of the calculated electronic absorption spectrum of polymorph II was carried out in order to assign the observed electronic transitions and to determine their character. A natural bonding orbital (NBO) analysis was executed at the same level to evaluate charge‐transfer, intramolecular hydrogen‐bonding interactions and hyperconjugative interactions. The third‐order nonlinear optical (NLO) properties of the compound were appraised by the ZINDO/sum‐over‐states method in both static and dynamic states. The orientationally averaged (isotropic) value of γ for the compound is greater than the corresponding value of 4‐nitroaniline (pNA).