Towards red-light o-carborane derivatives with both aggregation induced emission and thermally activated delayed fluorescence combining quantum chemistry calculation with molecular dynamics simulation

Abstract

We investigated a series of o-carborane derivatives and designed new red-light derivatives by combining DFT with MD simulation. The reason of their TADF was explored and the AIE property was analyzed in water, crystal and film surroundings.

Flexible and Transparent Oligothiophene-o-Carborane-Containing Hybrid Films for Nonlinear Optical Limiting Based on Efficient Two-Photon Absorption

“…Carborane (CB) has been regarded as an optical unit with good environmental stability, high electron-deficient and polarizable σ-aromatic character. , Many research works have introduced aryl groups (pyrenyl, fluorenyl, BODIPY, anthracenyl, etc.) into the o -CB cage to generate AIE-active systems. − Generally known, exhibited AIE properties could be attributed to the steric restriction of molecular motions and C 1 –C 2 bond vibration in the o -CB cage, and enhanced ICT processes are related to the rotation angles between the C 1 –C 2 bond and aryl substituents. − Despite extensively examination on the emission behavior of aryl-conjugated o -CB derivatives, the effect of various appended aryl units on photophysical properties of the AIE-emissive systems have rarely been investigated. Our group recently reported a series of fluorescent o -CB derivatives and explored their applications in detecting hazardous and volatile substances based on the stimuli-responsive film-based fluorescent sensors. − Meanwhile, as a model functional unit possessing high chemical stability, well-defined structure as well as outstanding electronic properties, oligothiophene derivatives offer diverse opportunities for molecularly engineered analogues with potential optoelectronic and photonic applications. − Kang et al prepared oligothiophene- o -CB derivatives substituted by electron-withdrawing dicyanovinyl group.…”

Highly Deformedo‐Carborane Functionalised Non‐linear Polycyclic Aromatics with Exceptionally Long C−C Bonds

“…Whenever molecular motion is restricted, however, carboranyl ICT states become more radiative. This often occurs upon aggregation, in a process known as aggregation induced emission (AIE) [7, 17, 18, 20–39] . o ‐Carborane is therefore considered an ‘AIE‐active element block’ [40]…”

“…This often occurs upon aggregation,i naprocess knowna sa ggregationi nduced emission (AIE). [7,17,18,[20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] o-Carborane is therefore considered an 'AIE-active element block'. [40] The AIE efficiency in carborane-containing fluorophores is enhanced when the rotation of the carboranei ss tructurally restricted around the ICT geometry (i.e.,w hen the C C ÀC C bond is approximately perpendicular to plane of the fluorophore).…”

Synthesis and Structure of an o‐Carboranyl‐Substituted Three‐Coordinate Borane Radical Anion

“…[77][78][79][80][81][82][83] The ortho-isomer is a rotation-dependent π-acceptor, accepting electron density into its C1À C2 σ*-anti-bonding orbital, often leading to aggregation-induced emission (AIE). [84][85][86][87][88][89][90][91][92][93][94][95][96][97][98] Both aspects provide opportunities for novel material design. Closerange conjugation of a carboranyl moiety to a 3-coordinate boron has rarely been studied.…”

“…They are unique building blocks in optoelectronic materials with high thermal stability due to their 3‐dimensional aromaticity [77–83] . The ortho ‐isomer is a rotation‐dependent π ‐acceptor, accepting electron density into its C1−C2 σ *‐anti‐bonding orbital, often leading to aggregation‐induced emission (AIE) [84–98] . Both aspects provide opportunities for novel material design.…”