B–N Lewis Pair Functionalization of Anthracene: Structural Dynamics, Optoelectronic Properties, and O₂ Sensitization

Abstract

The judicial placement of main group elements in conjugated structures is emerging as a key route to novel functional hybrid materials. We demonstrate here that the formation of B-N Lewis pairs at the periphery of anthracene leads to buckling of the backbone while also dramatically lowering the LUMO energy. The resulting BN-substituted contorted polycyclic aromatic hydrocarbons show large bathochromic shifts in the absorption and emission relative to all-carbon analogs. In the presence of light, they rapidly react with O without the need for an external photosensitizer, resulting in selective and reversible formation of the corresponding endoperoxides.

Cleavage of Unstrained C−C Bonds in Acenes by Boron and Light: Transformation of Naphthalene into Benzoborepin

“…TheB (1) À N(1) and B(1) À C(1) bond lengths in 1a-1c are similar to that of B(ppy)Mes 2 (ppy = 2-phenylpyridine). [13] Compounds 1a-1d are stable in air and thermally stable up to 110 8 8Ci ns olution. This asymmetric arrangement of the mesityl groups plays ak ey role in the photoreactivity of this group of compounds,a s revealed by computational analysis presented below.Notably, the pyridyl ring and the naphthyl ring [defined by the plane of C(3), C(7), and C(10) atoms in 1a and 1c]inthese molecules are not coplanar and have adihedral angle of 30.2 (1a), 29.9 (1b), and 26.58 8 (1c), respectively.…”

Iodo‐Functionalized Salicylideneimine‐Boron Complexes: Synthesis and Photosensitized Degradation of Organic Water Pollutants

“…The overlap of the empty p‐orbital of boron with the organic moieties in such compounds leads to the delocalization of the electron cloud and planarization of the π‐systems, thereby resulting in interesting photophysical properties. Several tri‐ and tetra‐coordinated boron compounds have been synthesized by the complexation of boron with organic ligands containing hetero atoms . Four‐coordinate boron compounds based on an imine scaffold are reported to have higher stability compared with tricoordinate boron compounds .…”

“…Severalt ri-andt etra-coordinated boron compounds have been synthesized by the complexation of boron with organic ligands containing hetero atoms. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] Fourcoordinate boronc ompounds based on an imine scaffold are reported to have higher stabilityc ompared with tricoordinate boron compounds. [18] Although the luminescentp roperties of boranils are well documented, [18] the photosensitizationp rop-ertieso fs uch molecules have rarely been explored.…”

Structural Transformation in Metal–Organic Frameworks for Reversible Binding of Oxygen

“…[3] EPOs exhibit the exceptional performance of releasing oxygen, generally in the excited singlet state, under heating or ultra violet (UV) irradiation. [5] Therefore,t he reversible chemical binding of oxygen has significant advantages,such as better stability and more controllability,c ompared with physical adsorption. [5] Therefore,t he reversible chemical binding of oxygen has significant advantages,such as better stability and more controllability,c ompared with physical adsorption.…”

“…The EPOs of DPA-MOF,E PO-MOF,c an be obtained by the [4+ +2]-cycloaddition with 1 O 2 ,w hich was produced by5,10,15, under irradiation of 660 nm light-emitting diode (LED). The EPOs of DPA-MOF,E PO-MOF,c an be obtained by the [4+ +2]-cycloaddition with 1 O 2 ,w hich was produced by5,10,15, under irradiation of 660 nm light-emitting diode (LED).…”