5 research outputs found
Trifid or double-notched aortic Doppler: an aortic âTrishulaâ sign
Trifid or double-notched aortic Doppler: an aortic âTrishulaâ sig
At the Borderline between MetalâMetal Mixed Valency and a Radical Bridge Situation: Four Charge States of a Diruthenium Complex with a Redox-Active Bis(<i>mer</i>-tridentate) Ligand
The
complex ions [L<sup>3</sup>RuÂ(ÎŒ,η<sup>3</sup>:η<sup>3</sup>-BL)ÂRuL<sup>3</sup>]<sup><i>n</i>+</sup> (<b>1</b><sup><b><i>n</i>+</b></sup>, L<sup>3</sup> = 4,4âČ,4âł-tri-<i>tert</i>-butyl-2,6,2âČ,6âł-terpyridine
and H<sub>2</sub>BL<sup>2â</sup> = 1,2-bisÂ(salicyloyl)Âhydrazide(2â))
were isolated with PF<sub>6</sub><sup>â</sup> or ClO<sub>4</sub><sup>â</sup> counterions (<i>n</i> = 1) and as bisÂ(hexafluorophosphate)
(<i>n</i> = 2). Structural, electrochemical, and spectroscopic
characterization reveals the monocation as intermediate (<i>K</i><sub>c</sub> = 10<sup>8.2</sup>) in the three-step reversible redox
system <b>1</b><sup><b>0/+/2+/3+</b></sup>. The <b>1</b><sup><b>+</b></sup> ion has the molecule-bridged (Ru-âŻ-âŻ-Ru
4.727 Ă
) ruthenium centers involved in five- and six-membered
chelate rings, and it exhibits long-wavelength absorptions at λ<sub>max</sub> 2240, 1660, and 1530 nm (Δ<sub>max</sub> = 1000,
3000, and 8000 M<sup>â1</sup> cm<sup>â1</sup>, respectively),
which would be compatible with a Ru<sup>III</sup>Ru<sup>II</sup> mixed-valent
situation or with a coordinated radical ion bridge. In fact, EPR and
DFT analysis of <b>1</b><sup><b>+</b></sup> reveals that
the spin is equally distributed over the ligand bridge and over both
metals. The oxidized paramagnetic ions <b>1</b><sup><b>2+</b></sup> and <b>1</b><sup><b>3+</b></sup> have been studied
by <sup>1</sup>H NMR and EPR and by TD-DFT supported UVâvisâNIR
and MIR (mid-IR) spectroelectrochemistry. The capacity of various
kinds of bisÂ(<i>mer</i>-tridentate) bridging ligands (Ï
donors or Ï acceptors, cyclometalated or noncyclometalated)
for mediating metalâmetal interactions is discussed
Molecular Engineering of Self-Assembling Diphenylalanine Analogues Results in the Formation of Distinctive Microstructures
Diphenylalanine
is one of the most studied building blocks in organic
supramolecular chemistry, forming ordered assemblies with unique mechanical,
optical, piezoelectric, and semiconductive properties. These structures
are being used for diverse applications, including energy storage,
biosensing, light emission, drug delivery, artificial photosynthesis,
and chemical propulsion. To increase the structural diversity of this
dipeptide building block, three previously unreported analogues in
which the aliphatic chain between the peptide backbone and the phenyl
ring was gradually lengthened were synthesized. Each dipeptide self-assembled
into unique microstructures, differing in morphology, which ranged
from flat plates to long microrods to flattened microplanks. The structures
were also found to possess distinctive optical properties. Furthermore,
X-ray crystallography of each of the three diphenylalanine analogues
presented distinctive molecular arrangements. The remarkable differences
between each dipeptide in the intermolecular interactions they formed
provide insight into the physicochemical mechanisms of self-assembly
and, in addition, indicate the biological significance of the single
methylene bridge of phenylalanine
Molecular Engineering of Self-Assembling Diphenylalanine Analogues Results in the Formation of Distinctive Microstructures
Diphenylalanine
is one of the most studied building blocks in organic
supramolecular chemistry, forming ordered assemblies with unique mechanical,
optical, piezoelectric, and semiconductive properties. These structures
are being used for diverse applications, including energy storage,
biosensing, light emission, drug delivery, artificial photosynthesis,
and chemical propulsion. To increase the structural diversity of this
dipeptide building block, three previously unreported analogues in
which the aliphatic chain between the peptide backbone and the phenyl
ring was gradually lengthened were synthesized. Each dipeptide self-assembled
into unique microstructures, differing in morphology, which ranged
from flat plates to long microrods to flattened microplanks. The structures
were also found to possess distinctive optical properties. Furthermore,
X-ray crystallography of each of the three diphenylalanine analogues
presented distinctive molecular arrangements. The remarkable differences
between each dipeptide in the intermolecular interactions they formed
provide insight into the physicochemical mechanisms of self-assembly
and, in addition, indicate the biological significance of the single
methylene bridge of phenylalanine