Chirogenesis and Pfeiffer Effect in Optically Inactive EuIII and TbIII Tris(β-diketonate) Upon Intermolecular Chirality Transfer From Poly- and Monosaccharide Alkyl Esters and α-Pinene: Emerging Circularly Polarized Luminescence (CPL) and Circular Dichroism (CD)

Abstract

We report emerging circularly polarized luminescence (CPL) at 4f-4f transitions when lanthanide (Eu III and Tb III) tris(β-diketonate) embedded to cellulose triacetate (CTA), cellulose acetate butyrate (CABu), D-/L-glucose pentamethyl esters (D-/L-Glu), and D-/L-arabinose tetramethyl esters (D-/L-Ara) are in film states. Herein,

Synchronization in Non-Mirror-Symmetrical Chirogenesis: Non-Helical π–Conjugated Polymers with Helical Polysilane Copolymers in Co-Colloids

“…The most important term in the C-H/π interactions between soft-base and soft-acid hydrogen bonding is the London dispersion force; nature favors delocalization by compensating opposite charges on atoms and groups tempo-spatially generated by a quantum fluctuation. Mulliken charge neutrality hypothesis proposed by us is applicable to various complex systems [23,24]; the hypothesis is similar to an exact charge neutrality of Coulombic interaction that is the key concept of a spontaneous association resulting from a long-range attractive force between polycations and polyanions [17]. The oppositely signed, but permanent Mulliken charges on atoms (marked as green and red color atoms) can feel intense attractive forces each other.…”

“…In 2000 and 2004, Borovkov and Inoue coined the term chirogenesis to account for MSB phenomena observed for supramolecular chirality induction of achiral bisporphyrins endowed with several chiral amines and chiral alcohols in solutions [21,22]. MSB plays a key role in providing various chiroptical functionalities and sensing [21][22][23][24]. The generality of chirogenesis unifying attractive/repulsive intermolecular chirality transfer capability should be widely applicable to binary colloidal polymer systems upon non-covalent interactions by assorting multiple non-charged, less-polar polymers: e.g., (i) achiral polymer and chiral polymer, (ii) non-helical polymer and helical polymer, and, more in general (iii) optically inactive polymer and optically active polymer.…”

Circular Polarization of Luminescence as a Tool To Study Molecular Dynamical Processes

“…[117][118][119][120] The lanthanide ions may be complexed directly to the molecule of interest, for instance in studies of metal binding proteins [121,122] and nucleic acids. [123] Alternatively, one can also use specific lanthanide chelates to probe nucleic acids, [124][125][126] amino acids, [127][128][129][130] proteins [131,132] and sugars [133][134][135] In these studies one has to rely on relatively strong interaction of the lanthanide chelate with the analyte to induce some change in the transition probabilities of the lanthanide ion. Using lanthanide chelates one can also go one step further and probe even weaker binding events by making use of energy and/or electron transfer processes with the analyte.…”

Resonance in Chirogenesis and Photochirogenesis: Colloidal Polymers Meet Chiral Optofluidics

“…In an analogy to achiral photoluminescence excitation (PLE) spectroscopy, CPLE spectroscopy provides differences in absorption band profiles in the ground state responsible for the specific CPL signals in the photoexcited state solely by monitoring, at a specific CPL band, as a function of wavelength in a vacuum. Although CPLE spectroscopy is rare in the realm of chiroptical spectroscopy, we often apply this technique to clarify which unpolarized absorption and CD bands are responsible for CPL/PL bands, particularly, dual/multiple CPL bands with opposite chiroptical signs [185]. Importantly, CPL, CPLE, PL, and PLE spectroscopy cannot apply to non-luminescent and ultraweak luminescent chromophores.…”