Water molecular bridge-induced selective dual polarization in crystals for stable multi-emitters.

In the solid state, the molecular polarization of donor-acceptor (D-A) molecules can be implemented in a simple way the use of an external polarizing source (, an electric field). However, internal chemical polarization approaches are less studied due to difficulties related to controlling the charge-separation orientation in the solid state. Herein, a series of D-A molecules with both a proton donor and an acceptor were designed. Water-based molecular bridges were then established in their crystal structures, which firmly and alternately connected the proton donor of one molecule and the acceptor of another an intermolecular H-bond network. In this way, the selective dual polarization of a phenolic hydroxyl group and a pyridinyl group could be achieved, owing to the strengthening of the charge-separation orientation upon the simultaneous deprotonation and protonation of the D-A molecules. This effect led to a 3-5-fold amplification of the molecular dipole moment in the crystal form relative to the monomeric state. On this basis, multi-excitation and multi-emission characteristics were achieved in these charge-separated crystals, endowing them with the ability to visually detect the energy of a light source, covering a wide range of the UV-Vis spectral region. This work provides a practical chemical approach for developing intrinsically polarized systems that can exhibit stable but distinct molecular photophysical properties.