Blue‐to‐Orange Color‐Tunable Laser Emission from Tailored Boron‐Dipyrromethene Dyes

Abstract

A series of meso-substituted boron-bipyrromethene (BODIPY) dyes are synthesized and their laser and photophysical properties systematically studied. Laser emission covering a wide visible spectral region (from blue to orange) is obtained by just changing the electron donor character of the heteroatom at position 8. The additional presence of methyl groups at positions 3 and 5 results in dyes with a photostability similar to that of the unsubstituted dye but with much improved efficiency. Correlation of the lasing properties of the different dyes to their photophysical properties provides inklings to define synthetic strategies of new BODIPY dyes with enhanced efficiency and modulated wavelength emission over the visible spectral region.

Rapid and Selective Electrophilic Trifluoromethylation of the 4,4‐Difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) Scaffold

“…In addition, fluorescence quantum yields of Φ F ( 9 ) THF = 0.0244 and 0.0237 against the standards 9,10‐diphenylanthracene and perylene, respectively, were obtained, which contrast the reported value of Φ F ( 2 ) MeOH = 0.15 of the parent structure. Indeed, this result further corroborates the electron‐deficient nature of 9 , as quenching of the excited state by intramolecular charge transfer from the meso heteroatom is expected to become more favorable 25. Finally, in agreement with Kasha's rule,26 if the excitation wavelength was set to 387 nm, the main emission was still centered around 524 nm, which corresponds to a pseudo‐Stokes shift of Δ S = 137 nm.…”

Synthesis, Properties, and Functionalization of Nonsymmetric 8‐MethylthioBODIPYs

“…Such a group (compound 2 ) should lead to a spectral bathochromic shift relative to the reference compound 1 owing to the LUMO stabilization caused by the inductive electron‐withdrawing character of the sulfur atom. Nonetheless, the feasible electronic coupling of the methylthio group with the indacene core provides an alternative delocalized π system (Figure ) . As a consequence, the absorption spectrum consists of two bands (or shoulders, depending on the alkylation of the dipyrrin core, as is discussed later) corresponding to the stabilization of each mesomeric form: the long‐wavelength band from the cyanine‐like delocalization expected for BODIPYs, and the short‐wavelength band that results from the selective electronic coupling of the methylthio group with one chomophoric pyrrole (Figure ).…”

“…The presence of heteroatoms at the meso position produces remarkable changes in the spectroscopic signatures of the BODIPYs, which can be modulated in terms of electronegativity . In this section we focus in particular on the influence of the 8‐methylthio group.…”

Spectroscopic characterization of synthetic heteroatom-functionalized fluorescent probes for bioimaging / Sentetik heteroatom-fonksiyonelize floresans probların biyogörüntüleme uygulamaları için spektroskopik karakterizasyonu

“…BODIPYs are usually amenable for functionalization at all positions on the main core such as introducing ethynyl, halogens, methyl or aromatic groups onto the system [6][7][8][9][10][11][12]. The nucleophilic substitution reaction to functionalize the BODIPY core at 3-and 5-position is an easy synthetic approach to change the spectroscopic properties of the BODIPY compound [10,[13][14][15][16][17][18][19][20][21][22][23][24]. According to recent literature, very few amine or heteroatom-based BODIPY compounds have been prepared and reported at 3-or 5-position on BODIPY core [10,[13][14][15][24][25][26][27].…”

“…The nucleophilic substitution reaction to functionalize the BODIPY core at 3-and 5-position is an easy synthetic approach to change the spectroscopic properties of the BODIPY compound [10,[13][14][15][16][17][18][19][20][21][22][23][24]. According to recent literature, very few amine or heteroatom-based BODIPY compounds have been prepared and reported at 3-or 5-position on BODIPY core [10,[13][14][15][24][25][26][27]. In addition to halogens, methyl or formyl or amine functional groups can be easily synthesized and activated to proteins or other biological systems [24,[28][29][30].…”