2 research outputs found
Electrophilic Reactivity of Tetrabromorhodamine 123 is Bromine Induced: Convergent Interpretation through Complementary Molecular Descriptors
Nucleophilic
addition of water and of methanol to 3,6-diamino-2,4,5,7-tetrabromo-9-[2-(methoxycarbonyl)
phenyl]-9<i>H</i>-xanthen-9-ylium, 4BrR123, yields respectively
2-(3,6-diamino-2,4,5,7-tetrabromo-9-hydroxy-9<i>H</i>-xanthen-9-yl)xanthyl
benzoate, HO4BrR123 and 2-(3,6-diamino-2,4,5,7-tetrabromo-9-methoxy-9<i>H</i>-xanthen-9-yl)xanthyl benzoate, MeO4BrR123. The novel experimental
results are addressed theoretically. The linear free energy relationship,
LFER, second-order perturbation theory analysis of the natural bond
orbital, NBO, and quantum theory of atoms in molecules, QTAIM, lead
to the same conclusion: the electron-withdrawing effect of bonded
Br atoms in 4BrR123 extremely enhances the molecular electrophilicity,
as compared to 3,6-diamino-9-[2-(methoxycarbonyl) phenyl]-9<i>H</i>-xanthen-9-ylium, R123. The reactivity of these diaminoxanthylium
cations is discussed in the context of local and global softness in
extended conjugated systems
Reorganization of Self-Assembled Dipeptide Porphyrin J-Aggregates in Water–Ethanol Mixtures
The self-assembly of a neutral <i>meso</i>-methoxyphenylporphyrin
functionalized with a dipeptide glycilglycine substituent (MGG) in
water and in water–ethanol mixtures was studied by absorption
and fluorescence spectroscopy. In water, hydrophobic interactions
and the noncovalent intermolecular hydrogen bonding between the terminal
carboxylate group of one porphyrin and the hydrogen atoms of the pyrrolic
nitrogens of another porphyrin originate nonspecific disorganized
H- and J-aggregates. The addition of ethanol (0.1–25% v/v)
to the water creates small clusters within which porphyrin J-aggregates
reorganize as revealed by a narrow intense band detected by the Rayleigh
light scattering (RLS) at 443 nm. Similar phenomenology is detected
in SDS premicellar aggregates. Computational DFT calculations of a
model dimer formation stabilized via intermolecular hydrogen bonding
estimate an energy gain of −22 kJ mol<sup>–1</sup> and
a center-to-center and interplane distances between porphyrin moieties
of 16.8 and 3.7 Å, respectively. The kinetics of the J-aggregate
formation could be fitted with a time-dependent model, and an activation
energy of 96 kJ mol<sup>–1</sup> was estimated. The aggregate's
morphology of MGG was followed by transmission electron microscopy
(TEM) which showed rod-type structures of 5–8 μm evolving
to spherical particles with increased ethanol content. Similar images
and sizes were obtained in analogous samples using fluorescence lifetime
imaging microscopy (FLIM) and dynamic light scattering (DLS). The
formation of excitonically coupled supramolecular MGG structures of
brickwork or staircase types is proposed in these water–ethanol
mixtures