370
Y. Morisaki
instead of chromatographic resolution by chiral columns. A wide variety of optically active π-stacked molecules, cyclic molecules, oligomers, and polymers were
prepared using the obtained enantiopure disubstituted and tetrasubstituted [2.2]paracyclophanes as chiral building blocks. They were used to construct the chiral higherordered structures such as V-shaped, X-shaped, propeller-shaped, triangle-shaped,
and double helical structures both in the ground and excited states due to the structurally stable planar chiral cyclophanes. This is important to show excellent CPL
performance. [2.2]Paracyclophane-based molecules exhibit good PL property with
high Φ PL . Their ε values are large because of the extended π-electron systems.
Generally, it is difficult to produce the materials emitting intense CPL with high Φ PL
and large g lum . The planar chiral [2.2]paracyclophane skeleton seems to be an ideal
scaffold for developing materials exhibiting strong CPL.
References
Aly AA, Brown AB (2009) Asymmetric and fused heterocycles based on [2.2]paracyclophane.
Tetrahedron 65:8055–8089
Amako T, Nakabayashi K, Mori T, Inoue Y, Fujiki M, Imai Y (2014) Sign inversion of circularly
polarized luminescence by geometry manipulation of four naphthalene units introduced into a
tartaric acid scaffold. Chem Commun 50:12836–12839
Bartholomew GP, Bazan GC (2001) Bichromophoric paracyclophanes: models for interchromophore delocalization. Acc Chem Res 34:30–39
Bazan GC (2007) Novel organic materials through control of multichromophore interactions. J Org
Chem 72:8615–8635
Bazan GC, Oldham WJ, Lachicotte RJ, Tretiak S, Chernyak V, Mukamel S (1998) Stilbenoid dimers:
dissection of a paracyclophane chromophore. J Am Chem Soc 120:9188–9204
Berova N, Nakanishi K, Woody RW (eds) (2000) Circular dichroism, 2nd edn. Wiley-VCH, Toronto
Braddock DC, MacGilp ID, Perry BG (2002) Improved synthesis of (±) -4,12dohydroxy[2.2]paracyclophane and its enantiomeric resolution by enzymatic methods: plana
chiral (r)- and (s)-phanol. J Org Chem 67:8679–8681
Brown CJ, Farthing AC (1949) Preparation and structure of di-p-xylylene. Nature 164:915–916
Chem N, Yan B (2018) Recent theoretical and experimental progress in circularly polarized
luminescence of small organic molecules. Molecules 23:3376/1–32
Chow HF, Low KH, Wong KY (2005) An improved method for the regiospecific synthesis of
polysubstituted [2.2]paracyclophanes. Synlett 2130–2134
Clayden J (2002) In organolithiums: selectivity for synthesis. Pergamon, Oxford, pp 141–142
Cram DJ, Allinger NL (1955) Macro rings. xii. stereochemical consequences of steric compression
in the smallest paracyclophane. J Am Chem Soc 77:6289–6294
Cram DJ, Steinberg H (1951) Macro rings. i. preparation and spectra of the paracyclophanes. J Am
Chem Soc 73:5691–5704
Emeris CA, Oosterhoff LJ (1967) Emission of circularly-polarized radiation by optically-active
compounds. 1:129–132
Field JE, Muller G, Riehl JP, Venkataraman D (2003) circularly polarized luminescence from
bridgedtriarylamine helicenes. J Am Chem Soc 125:11808–11809
Fréchet JMJ (1994) Functional polymers and dendrimers: reactivity, molecular architecture, and
interfacial energy. Science 263:1710–1715
Gibson SE, Knight JD (2003) [2.2]Paracyclophane derivatives in asymmetric catalysis. Org Biomol
Chem 1:1256–1269
Y. Morisaki
instead of chromatographic resolution by chiral columns. A wide variety of optically active π-stacked molecules, cyclic molecules, oligomers, and polymers were
prepared using the obtained enantiopure disubstituted and tetrasubstituted [2.2]paracyclophanes as chiral building blocks. They were used to construct the chiral higherordered structures such as V-shaped, X-shaped, propeller-shaped, triangle-shaped,
and double helical structures both in the ground and excited states due to the structurally stable planar chiral cyclophanes. This is important to show excellent CPL
performance. [2.2]Paracyclophane-based molecules exhibit good PL property with
high Φ PL . Their ε values are large because of the extended π-electron systems.
Generally, it is difficult to produce the materials emitting intense CPL with high Φ PL
and large g lum . The planar chiral [2.2]paracyclophane skeleton seems to be an ideal
scaffold for developing materials exhibiting strong CPL.
References
Aly AA, Brown AB (2009) Asymmetric and fused heterocycles based on [2.2]paracyclophane.
Tetrahedron 65:8055–8089
Amako T, Nakabayashi K, Mori T, Inoue Y, Fujiki M, Imai Y (2014) Sign inversion of circularly
polarized luminescence by geometry manipulation of four naphthalene units introduced into a
tartaric acid scaffold. Chem Commun 50:12836–12839
Bartholomew GP, Bazan GC (2001) Bichromophoric paracyclophanes: models for interchromophore delocalization. Acc Chem Res 34:30–39
Bazan GC (2007) Novel organic materials through control of multichromophore interactions. J Org
Chem 72:8615–8635
Bazan GC, Oldham WJ, Lachicotte RJ, Tretiak S, Chernyak V, Mukamel S (1998) Stilbenoid dimers:
dissection of a paracyclophane chromophore. J Am Chem Soc 120:9188–9204
Berova N, Nakanishi K, Woody RW (eds) (2000) Circular dichroism, 2nd edn. Wiley-VCH, Toronto
Braddock DC, MacGilp ID, Perry BG (2002) Improved synthesis of (±) -4,12dohydroxy[2.2]paracyclophane and its enantiomeric resolution by enzymatic methods: plana
chiral (r)- and (s)-phanol. J Org Chem 67:8679–8681
Brown CJ, Farthing AC (1949) Preparation and structure of di-p-xylylene. Nature 164:915–916
Chem N, Yan B (2018) Recent theoretical and experimental progress in circularly polarized
luminescence of small organic molecules. Molecules 23:3376/1–32
Chow HF, Low KH, Wong KY (2005) An improved method for the regiospecific synthesis of
polysubstituted [2.2]paracyclophanes. Synlett 2130–2134
Clayden J (2002) In organolithiums: selectivity for synthesis. Pergamon, Oxford, pp 141–142
Cram DJ, Allinger NL (1955) Macro rings. xii. stereochemical consequences of steric compression
in the smallest paracyclophane. J Am Chem Soc 77:6289–6294
Cram DJ, Steinberg H (1951) Macro rings. i. preparation and spectra of the paracyclophanes. J Am
Chem Soc 73:5691–5704
Emeris CA, Oosterhoff LJ (1967) Emission of circularly-polarized radiation by optically-active
compounds. 1:129–132
Field JE, Muller G, Riehl JP, Venkataraman D (2003) circularly polarized luminescence from
bridgedtriarylamine helicenes. J Am Chem Soc 125:11808–11809
Fréchet JMJ (1994) Functional polymers and dendrimers: reactivity, molecular architecture, and
interfacial energy. Science 263:1710–1715
Gibson SE, Knight JD (2003) [2.2]Paracyclophane derivatives in asymmetric catalysis. Org Biomol
Chem 1:1256–1269