π-Extended ‘Push-pull’ corroles (D-π-A) are generally utilized to design molecules with large values of first and second hyperpolarizabilities (β and γ).1 These molecular systems depict strong charge transfer characteristics between electron donor and acceptor groups, which usually enhance the nonlinear optical (NLO) properties.2 Corrole and porphyrin derivatives are found to exhibit noteworthy NLO properties accompanied by an ultrafast (picosecond-femtosecond) response.3–5 An efficient pull-push β-dicyanobutadiene substituted Co(III) corrole derivatives (Scheme 1) were synthesized using Knoevenagel condensation reaction to introduce β-dicyanobutadiene substituents in very good yield and were characterized by various spectroscopic techniques. The UV-vis spectrum of the complexes exhibited a broadening and red shift in the Soret Band, together with a very significant increase of the Q band intensity. DFT studies revealed that β-substituents are planar with macrocyclic core due to extended π-conjugation. Their ultrafast nonlinear optical and transient absorption (TA) spectroscopic properties has been explored further. We achieved high value of nonlinear absorption and refractive index coefficient. Here, we have achieved the magnitude of β in order ~ 10-13m2W-1 and n2 in magnitudes of ~ 10-19m2W-1.

π-Extended ‘Push-pull’ corroles (D-π-A) are generally utilized to design molecules with large values of first and second hyperpolarizabilities (β and γ).1 These molecular systems depict strong charge transfer characteristics between electron donor and acceptor groups, which usually enhance the nonlinear optical (NLO) properties.2 Corrole and porphyrin derivatives are found to exhibit noteworthy NLO properties accompanied by an ultrafast (picosecond-femtosecond) response.3–5 An efficient pull-push _β_-dicyanobutadiene substituted Co(III) corrole derivatives (Scheme 1) were synthesized using _Knoevenagel condensation reaction to introduce _β_-dicyanobutadiene substituents in very good yield and were characterized by various spectroscopic techniques. The UV-vis spectrum of the complexes exhibited a broadening and red shift in the Soret Band, together with a very significant increase of the Q band intensity. DFT studies revealed that β-substituents are planar with macrocyclic core due to extended π-conjugation. Their ultrafast nonlinear optical and transient absorption (TA) spectroscopic properties has been explored further. We achieved high value of nonlinear absorption and refractive index coefficient. Here, we have achieved the magnitude of β in order ~ 10-13m2W-1 and n2 in magnitudes of ~ 10-19m2W-1._

Synthesis of π-Extended ‘Push-Pull’ CoIII Corroles for NLO Applications

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27th CRSI National Symposium in Chemistry

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