Semiconductors group

Abstract:

The smallest and most strained member of a family of π-conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene. Both templates are effective for directing the synthesis of the butadiyne-linked cyclic pentamer, despite the fact that the radii of their N5 donor sets are too small by 0.5 Å and 0.9 Å, respectively (from DFT calculations). The five-porphyrin nanoring exhibits a structured absorption spectrum and its fluorescence extends to 1200 nm, reflecting strong π conjugation and Herzberg-Teller vibronic coupling.

Abstract:

The smallest and most strained member of a family of π‐conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene. Both templates are effective for directing the synthesis of the butadiyne‐linked cyclic pentamer, despite the fact that the radii of their N5 donor sets are too small by 0.5 Å and 0.9 Å, respectively (from DFT calculations). The five‐porphyrin nanoring exhibits a structured absorption spectrum and its fluorescence extends to 1200 nm, reflecting strong π conjugation and Herzberg–Teller vibronic coupling.

Abstract:

Supramolecular antenna-ring complexes are of great interest due to their presence in natural light-harvesting complexes. While such systems are known to provide benefits through robust and efficient energy funneling, the relation-ship between molecular structure, strain (governed by nuclear co-ordinates and motion) and energy dynamics (arising from electronic behavior) is highly complex. We present a synthetic antenna-nanoring system based on a series of conjugated porphyrin chromophores ideally suited to explore such effects. By systematically varying the size of the acceptor nanoring, we reveal the interplay between antenna-nanoring binding, local strain and energy dynamics on the picosecond timescale. Binding of the antenna unit creates a local strain in the nanoring, and this strain was measured as a function of the size of the nanoring, by UV-vis-NIR titration, providing information on the conformational flexibility of the system. Strikingly, the energy transfer rate is independent of nanoring size, indicating the existence of strain-localized acceptor states, spread over about six porphyrin units, arising from the non-covalent antenna-nanoring association.