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Transfer of Chirality for Memory and Separation

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Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 298))

Abstract

Transfer of chirality is an intriguing issue worth studying to understand better the origin of life and for possible technological applications. In the last few years we have been working in this area studying the chain of events that begins with induction, reaches a permanent transfer (chiral memory) and extends in some cases to a (quasi-)reversible situation in which induced and permanently memorized chirality coexists. This can happen thanks to a designed blend of thermodynamics and kinetics.

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Notes

  1. 1.

    On the contrary, no CD signal is observed when the two porphyrins are mixed in pure water (pH 2.3).

  2. 2.

    The formation of the J aggregates is hierarchically controlled. The only way to obtain these species is by allowing porphyrin aggregation with Λ− or Δ−[Ru(phen)3]2+ at a pH value of around 6 and then decreasing the pH to 2.5.

  3. 3.

    The CD signal of the (Δ−[Ru(phen)3]2+/H2TPPS) complex is absent because the formation of the complex is slow. The signal appears after 10–15 min.

  4. 4.

    Memory of chirality is lost if the pH value is raised to 8.

  5. 5.

    After about five pH cycles the solution becomes milky and scatters because of the formation of extended aggregates: this causes a decrease of the CD intensity.

  6. 6.

    Melting experiments were also performed: the ICD of Λ− or Δ−[Ru(phen)3]2+/J aggregates disappears at around 90°C. By lowering temperature at 25°C we have obtained the starting signal shape.

  7. 7.

    If chirality is induced at the assembling onset then they will “remember” the shape during their growth leading to chiral amplification [46].

  8. 8.

    This is also the most common situation owing to the “impossibility” to get pure water.

  9. 9.

    The UV part of the CD spectrum, reporting [Ru(Phen)3]2+ chirality, is not affected by stirring confirming that ruthenium complexes are free in solution and not part of the J-aggregates. Also for the analogous system with the Λ enantiomer no deposition of the Δ enantiomer is observed in spite of the CW stirring.

  10. 10.

    Following suggestions from a referee we have halved the cuvettes. Both faces show CD signals which have the same shape as that of the empty cuvette: this enables LD contributions to be excluded.

  11. 11.

    Δ- or Λ-[Ru(Phen)3]2+ are free in solution (10 mm): therefore they can drive a preferential chiral aggregation despite the vortex chirality.

Abbreviations

AuT4:

Au-meso-tetrakis(4-N-methylpyridyl)porphyrin

CCW:

Counter clock wise

CD:

Circular dichroism

cis-DPPS:

5,10-Bis(4-sulfonatophenyl)-15,20-diphenylporphyrin

CuT4:

Cu-meso-tetrakis(4-N-methylpyridyl)porphyrin

CuTPPS:

Cu-meso-tetrakis(4-sulphonatophenyl)porphyrin

CW:

Clock wise

DLS:

Dynamic light scattering

EDXD:

Energy dispersive X-ray diffraction

ELS:

Elastic light scattering

H2T4:

meso-Tetrakis(4-N-methylpyridyl)porphyrin

H2TPPS:

meso-Tetrakis (4-sulphonatophenyl)porphyrin

H2TpyP:

meso-Tetrakis (4-phenyl)porphyrin

ICD:

Induced circular dichroism

LD:

Linear dichroism

MnT4:

Mn-meso-tetrakis(4-N-methylpyridyl)porphyrin

MT4:

meso-Tetrakis(4-N-methylpyridyl)porphyrin metallo derivative

MTPPS:

meso-Tetrakis(4-sulphonatophenyl)porphyrin metallo derivative

Mw:

Molecular weight

Phe:

Phenylalanine

RLS:

Resonance light scattering

Ru[(Phen)3]2+ :

Ru[(phenanthroline)3]2+

trans-DPPS:

5,15-Bis(4-sulfonatophenyl)-10,20-diphenylporphyrin

ZnT4:

Zn-meso-tetrakis(4-N-methylpyridyl)porphyrin

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Authors and Affiliations

  1. C.N.R, Istituto di Biostrutture e Bioimmagini-Sezione di Catania, Viale A. Doria 6, 95125, Catania, Italy

    Rosaria Lauceri

  2. Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, 95125, Catania, Italy

    Alessandro D’Urso, Angela Mammana & Roberto Purrello

Authors
  1. Rosaria Lauceri
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  2. Alessandro D’Urso
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  3. Angela Mammana
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  4. Roberto Purrello
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Corresponding author

Correspondence to Roberto Purrello .

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Editors and Affiliations

  1. Dept. Chemical Physics, Weizmann Institute of Science, Rehovot, Israel

    Ron Naaman

  2. Duke University, Fitzpatrick Institute for Photonics, 101 Science Drive, Durham, NC, 27708, USA

    David N Beratan

  3. Chevron Science Center, Department of Chemistry, University of Pittsburgh, Parkman Avenue 219, Pittsburgh, 15260, Pennsylvania, USA

    David Waldeck

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Lauceri, R., D’Urso, A., Mammana, A., Purrello, R. (2010). Transfer of Chirality for Memory and Separation. In: Naaman, R., Beratan, D., Waldeck, D. (eds) Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures. Topics in Current Chemistry, vol 298. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2010_87

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