title: Computational design of improved two-photon active caging compounds based on nitrodibenzofuran.
abstract: Nitrodibenzofuran (NDBF) has recently been established as photolabile protecting group and efficiently used as two-photon active cage. In this work, a computational approach is exploited to rationally design improved two-photon active caging groups based on this NDBF chromophore. For this objective, first the two-photon absorption (TPA) properties of NDBF are investigated in detail and a suitable theoretical approach for the reliable simulation of TPA spectra of this class of compounds is identified. Then, virtual chemical modifications are performed by introduction of substituents at the chromophore and replacement of the central furan ring by pyrolle, thiophene, and borrole heterocycles. Subsequently, the TPA properties of the resulting compounds are computed, and the influences of the chemical modifications on TPA properties investigated in detail. The most promising candidates with largely increased two-photon uncaging efficiencies are dimethylamino-substituted derivatives of NDBF, nitrodibenzopyrrol, and nitrodibenzothiophene.
authors.affiliation: Interdisciplinary Center of Scientific Computing, Ruprecht-Karls-University, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany. dreuw@uni-heidelberg.de
authors.forename: Andreas
authors.initials: A
authors.lastname: Dreuw
authors.forename: Matthias A
authors.initials: MA
authors.lastname: Polkehn
authors.forename: Robert
authors.initials: R
authors.lastname: Binder
authors.forename: Alexander
authors.initials: A
authors.lastname: Heckel
authors.forename: Stefan
authors.initials: S
authors.lastname: Knippenberg
mesh_terms: D001572:Benzofurans / Q000737:chemistry*; D003198:Computer Simulation; D006801:Humans; D008956:Models, Chemical; D015394:Molecular Structure; D017785:Photons; D011789:Quantum Theory
chemical_list: D001572:Benzofurans