Metal-Ion Sensing Fluorophores with Large Two-Photon Absorption Cross Sections:  Aza-Crown Ether Substituted Donor−Acceptor−Donor Distyrylbenzenes

• Published in: Journal of the American Chemical Society 2004-08, Vol.126 (30), p.9291-9306
• Main Authors: Pond, Stephanie J. K, Tsutsumi, Osamu, Rumi, Mariacristina, Kwon, Ohyun, Zojer, Egbert, Brédas, Jean-Luc, Marder, Seth R, Perry, Joseph W
• Format: Article
• Language: English
• Subjects: Aza Compounds - chemical synthesis; Aza Compounds - chemistry; Benzene Derivatives - chemistry; Chemistry; Crown Ethers - chemical synthesis; Crown Ethers - chemistry; Exact sciences and technology; Fluorescent Dyes - chemical synthesis; Fluorescent Dyes - chemistry; General and physical chemistry; Metals - chemistry; Microscopy, Confocal; Models, Chemical; Photons; Solution properties; Solutions; Spectrometry, Fluorescence
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja049013t

Chromophores based on a donor−acceptor−donor structure possessing a large two-photon absorption cross section and one or two mono-aza-15-crown-5 ether moieties, which can bind metal cations, have been synthesized. The influence of Mg2+ binding on their one- and two-photon spectroscopic properties has been investigated. Upon binding, the two-photon action cross sections at 810 nm decrease by a factor of up to 50 at high Mg2+ concentrations and this results in a large contrast in the two-photon excited fluorescence signal between the bound and unbound forms, for excitation in the range of 730 to 860 nm. Experimental and computational results indicate that there is a significant reduction of the electron donating strength of the aza-crown nitrogen atom(s) upon metal ion binding and that this leads to a blue shift in the position as well as a reduction in the strength of the lowest-energy two-photon absorption band. The molecules reported here can serve as models for the design of improved two-photon excitable metal-ion sensing fluorophores.