Abstract

Abstract As an advanced signal source, laser is very suitable for various photonic devices but implementing tunability of wavelength is more challenging. Herein, the study designs and synthesizes boron difluoride derivative tBuBF 2 , systematically studying the impact of assembly behavior on laser performance. The laser test results indicate that the emission wavelength of tBuBF 2 microcrystals can be controlled by varying the length of the microcrystals, with the shorter wavelength of 0–1 vibronic lasing emission at 444 nm and the longer wavelength of 0–2 lasing emission at 468 nm. Mechanistic studies reveal that laser color change comes from an increase in optical propagation losses due to self‐absorption at the 0–1 vibronic band. Furthermore, CBP@tBuBF 2 microcrystals constructed by doping with 4,4′‐bis(9‐carbazolyl)‐1,10‐biphenyl (CBP) as the guest molecule, which primarily exhibits 580 nm exciplex yellow emission while retaining weak blue emission. Moreover, it is demonstrated that the laser emission only occurred within the 0–2 vibronic band in the blue region owing to the increased self‐absorption phenomenon with 0–1 band, thus achieving controllable dual‐wavelength and exciplex emission for laser concealment. This work expands novel regulation strategy available for laser behavior control by enhancing the self‐absorption process, describing structure‐property relationships that will guide the design of advanced laser materials.