Organic solid‐state luminescence materials have shown great promise in many forefront areas of modern chemistry. However, the well‐developed organic luminescent solids usually provoke a mass of synthetic steps. To better utilize their performances, the development of simple strategies for host materials is a goal of general concern. Herein, a series of highly efficient solid‐state luminescence materials are attained with aid of one‐step acidification of commercially available molecules. The mechanism demonstrates that the luminous efficiency of the solid‐state molecules is efficiently improved due to the synergy from the emergence of cation–π interaction and the formation of excimer. The cation–π interaction replaces π–π packing, leading to the formation of dimers with higher rigidity in solid state accompanied by red‐shifted emissions. Therefore, this one‐step acidification design concept will light the great passion of scientists for the fabrication of cation−π‐triggered analogous organic solid‐state luminescence materials with different colors by changing the substituents on benzene moieties.
In this article, the structures and energies of CF3COCl in the low-lying electronic states have been determined by SA-2-CAS(8,7)/6-31G* and SA-2-MSPT2(8,7)/6-31G* calculations, which include equilibrium geometries, transition states, and three minimum-energy conical intersections (CI-1, CI-2, and CI-3) between S0 and S1 states. The AIMS method was used to carry out non-adiabatic dynamic simulations with the ab initio calculation performed at the SA-2-CAS(8,7)/6-31G* level. Upon irradiation to the S1 state, CF3COCl first relaxes to S1 minimum and then overcomes the ∼10 kcal/mol (TSS1_CCl) or ∼30 kcal/mol (TSS1_CO) barrier to the conical intersection region CI-1 or CI-3 (minor), with the S1 → S0 transition probability of 63:1. After non-adiabatic transition to the S0 state through CI-1, trajectories mainly distribute to three different reaction pathways, with one going back to S0 minimum through shortening of the C–Cl bond, the other forming CF3CO and Cl radicals by continuous elongation of the C–Cl distance, and another dissociating into CF3 + CO + Cl and running into the CI-3 region through elongation of C–C and C–Cl distances. Moreover, we found that the trajectories would recross to the S1 state with the recrossing probability of 13.9% through the CI-3 region due to the extremely sloped topographic character of CI-3. On the basis of time evolution of wavefunctions simulated here, the product ratio of CF3 + CO + Cl and CF3CO + Cl is 53.5%:18.4%, which is consistent with the experimental value of 3:1. We further explain the photo-dissociation wavelength dependence of CF3COCl, and the product ratio of CF3 + CO + Cl increases with the increase in total energy.
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