Photoluminescent and ferroelectric properties of a chiral rhenium(I) complex based on the chiral (−)-4,5-pinene-2,2′-bipyridine ligand

Electronic circular dichroism and circularly polarized luminescence acid-base switching activity is demonstrated in helicene-bipyridine proligand (1a) and in its “rollover” cycloplatinated derivative (2a). While proligand 1a displays a strong bathochromic shift (>160 nm) of the non polarized and circularly luminescence upon protonation, complex 2a displays slightly stronger emission. This striking different behavior between singlet emission in the organic helicene and triplet emission in the organometallic one is rationalized using theory. The very large bathochromic shift of the emission observed upon protonation of azahelicene-bipyridine 1a was rationalized by the decrease of aromaticity (promoting a charge transfer-type transition rather than a π–π* one) along with an increase of the HOMO-LUMO character of the transition and stabilization of the LUMO level upon protonation.

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Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes

Saleh

Moore

Srebro

et al. 2014

Chemistry A European J

176

116

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Dinuclear Rhenium Complexes with a Bridging Helicene‐bis‐bipyridine Ligand: Synthesis, Structure, and Photophysical and Chiroptical Properties

et al. 2020

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By attaching pyridine groups to a diaza[6]helicene, a helical, bisditopic, bis-N N-coordinating ligand can be accessed. Dinuclear rhenium complexes featuring this bridging ligand, of the form [{Re(CO) 3 Cl} 2 (N NÀ N N)], have been prepared and resolved to give enantiopure complexes. These complexes are phosphorescent in solution at room temperature under one-and twophoton excitation. Their experimental chiroptical properties (optical rotation, electronic circular dichroism and circularly polarized emission) have been measured. They show, for instance, emission dissymmetry factors of c.a. � 3x10 À 3. Quantum-chemical calculations indicate the importance of stereochemistry on the optical activity, pointing towards further design improvements in such types of complexes.

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Three Properties in One Coordination Complex: Chirality, Spin Crossover, and Dielectric Switching

Shi

et al. 2017

Eur J Inorg Chem

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In the search for multifunctional molecular materials, we designed an enantiopure pair of FeII complexes with chiral, chelating (R)/(S)‐4,5‐pinenepyridyl‐2‐pyrazine ligands exhibiting three inherent physical properties: chirality, spin crossover, and dielectric switching. The geometrical change resulted in coupling of the spin‐crossover transition at 187 K to dielectric switching. Both compounds were found to display light‐induced spin crossover that was thermally unstable above ca. 40 K. The coupling of two hysteretic properties, electric and magnetic, renders these compounds as potential switching devices.

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Photoluminescent and ferroelectric properties of a chiral rhenium(I) complex based on the chiral (−)-4,5-pinene-2,2′-bipyridine ligand

Cited by 11 publications

References 34 publications

Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes

Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes

Dinuclear Rhenium Complexes with a Bridging Helicene‐bis‐bipyridine Ligand: Synthesis, Structure, and Photophysical and Chiroptical Properties

Three Properties in One Coordination Complex: Chirality, Spin Crossover, and Dielectric Switching

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