Investigation of excited states of BODIPY derivatives and non-orthogonal dimers from the perspective of singlet fission.

We report state of the art electronic structure calculations RICC2 and XMCQDPT of BODIPY nonorthogonal dimers to understand the photophysical processes from the intramolecular singlet fission (iSF) perspective. We have calculated singlet, triplet and quintet states at the XMCQDPT(8,8)/cc-pVDZ level of theory and diabatic singlet states at the XMCQDPT(4,4)/cc-pVDZ level of theory. In all the systems studied, charge transfer states ((CA) and (AC)) couple strongly with locally excited ((SS)) and multiexcitonic ((TT)) states.

Acyl Transfer-Driven Rauhut-Currier Dimerization of Morita-Baylis-Hillman Ketones.

A serendipitous Rauhut-Currier dimerization of 1,1-disubstituted activated olefins derived from Morita-Baylis-Hillman adducts was observed in the presence of DABCO. The reaction is driven by the migration of an acyl group and produces multifunctionalized enol esters in yields greater than 90% in most cases, without necessitating column chromatographic purification. The acyl transfer is thought to proceed via a transition state typical of a Morita-Baylis-Hillman (MBH) reaction, supported by a brief mechanistic study involving computational calculations.