posted on 2020-03-02, 20:06authored byEkaterina
A. Dolgopolova, Anna A. Berseneva, Martín S. Faillace, Otega A. Ejegbavwo, Gabrielle A. Leith, Seok W. Choi, Haley N. Gregory, Allison M. Rice, Mark D. Smith, Maksymilian Chruszcz, Sophya Garashchuk, Karthikeyan Mythreye, Natalia B. Shustova
Photophysics tunability through alteration
of framework aperture
(metal–organic framework (MOF) = variable; guest = constant)
was probed for the first time in comparison with previously explored
concepts (MOF = constant; guest = variable). In particular, analysis
of the confinement effect on a photophysical response of integrated
5-(3-chlorobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (Cl-BI) chromophore allowed us to establish a photophysics–aperture
relationship. To shed light on the observed correlation, the framework
confined environment was replicated using a molecular cage, Pd6(TPT)4 (TPT = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine),
thus allowing for utilization of crystallography, spectroscopy, and
theoretical simulations to reveal the effect a confined space has
on the chromophore’s molecular conformation (including disruption
of strong hydrogen bonding and novel conformer formation) and any
associated changes on a photophysical response. Furthermore, the chosen
Cl-oHBI@Pd6(TPT)4 (Cl-oHBI = 5-(5-chloro-2-hydroxybenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one, chromophore) system was applied as a tool
for targeted cargo delivery of a chromophore to the confined space
of DNA, which resulted in promotion of chromophore–DNA interactions
through a well-established intercalation mechanism. Moreover, the
developed principles were applied toward utilizing a HBI-based chromophore
as a fluorescent probe on the example of macrophage cells. For the
first time, suppression of non-radiative decay pathways of a chromophore
was tested by anchoring the chromophore to a framework metal node,
portending a potential avenue to develop an alternative to natural
biomarkers. Overall, these studies are among the first attempts to
demonstrate the unrevealed potential of a confined scaffold environment
for tailoring a material’s photophysical response.