Panchromatic absorbers for solar light-harvesting

Abstract

A set of panchromatic absorbers exhibiting long excited-state lifetimes in both polar and nonpolar media has been prepared. The architectures are based on a porphyrin strongly coupled electronically to 1-4 perylene-monoimides via ethyne linkers. The constructs should find utility in molecular solar-conversion systems.

Accessing the Long-Lived Triplet Excited States in Transition-Metal Complexes: Molecular Design Rationales and Applications

“…Perylene bisimide (PBI) is a popular chromophore used in molecular assembly and studies of fluorescence . However, studies of the PBI triplet state are rare.…”

Synthesis of arrays containing porphyrin, chlorin, and perylene-imide constituents for panchromatic light-harvesting and charge separation

“…[13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] As one case in point, we recently developed a design motif that engenders panchromatic absorption yet affords a lowest singlet excited-state of discrete energy. 28,29 The motif relies on a perylene-monoimide attached to a porphyrin via an ethyne linker, where the linker joins the perylene 9-position and the porphyrin meso-position, both of which are sites of high electron density in the highest occupied molecular orbital (HOMO) of each constituent. Such a triad (PMI 2T P) composed of two perylene-monoimides tightly coupled electronically (via ethyne linkers) to one porphyrin is shown in Fig.…”

Exciton Migration and Surface Trapping for a Photonic Crystal Displaying Charge‐Recombination Fluorescence

“…Light‐harvesting antennae operate by arranging selected fluorophores in close proximity such that efficient electronic energy transfer (EET) can occur between neighbouring chromophores. Many artificial molecular arrays have been described that duplicate such EET processes . In a few cases, EET occurs over a dozen or so discrete subunits but this situation falls well short of what happens in natural systems, for which EET over hundreds, if not thousands, of chromophores is commonplace.…”

“…Many artificial molecular arraysh ave been describedt hat duplicates uch EET processes. [13][14][15][16] In af ew cases, EET occurs over ad ozen or so discrete subunits [17,18] but this situation falls well short of what happens in natural systems, for which EET over hundreds, if not thousands, of chromophores is commonplace. It seems doubtful that the same type of distributive patterns can be achieved by way of covalent chemistry and alternative ways to self-assemblea rtificial photon concentratorsa re needed.…”