Abstract

The molecular structure of 2,4-bis[6-(N-butyl-2,3,4-trihydroquinoloyl)]squaraine is centric, but its Langmuir–Blodgett films exhibit second-harmonic generation (SHG) with an effective monolayer susceptibility of 120 pm V-1 at 1.064 μm. This is not an inherent property of the molecule, and the intensity is too strong to be associated with the glass–monolayer interface. Instead, the SHG is attributed to a noncentrosymmetric aggregate structure and is enhanced by intermolecular charge transfer between the central acceptor and terminal donor of adjacent molecules. Electrospray ionization mass spectrometry has provided evidence of aggregation, even in very dilute solution, with the spectrum showing mass peaks that correspond to the monomer [mass/charge (m/z)=457, [M+H]+] and dimeric aggregate (m/z=913, [2M+H]+). These peaks persist in solid solution, and spin-coated films of the dye in poly(vinyl acetate) show weak SHG.

© 1998 Optical Society of America

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1997

G. J. Ashwell, G. M. S. Wong, D. G. Bucknall, G. S. Bahra, and C. R. Brown, “Neutron reflection from 2, 4-bis(4-(N-methyl-N-octylamino)phenyl)squaraine at the air–water interface and the linear and nonlinear optical properties of its Langmuir–Blodgett and spun-coated films,” Langmuir 13, 1629–1633 (1997).
[CrossRef]

1996

G. J. Ashwell, “Centrosymmetric molecules for second harmonic generation,” Adv. Mater. 8, 248–250 (1996).
[CrossRef]

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

H. J. Chen, K. Y. Law, and D. G. Whitten, “Aggregation of amphiphilic squaraines at the air–water interface and in Langmuir–Blodgett films,” J. Phys. Chem. 100, 5949–5955 (1996).
[CrossRef]

1995

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

1993

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

T. Geisler and T. Bjørnholm, “Second harmonic generation from different types of Langmuir–Blodgett films,” Synth. Met. 55/57, 3842–3847 (1993).
[CrossRef]

P. Hodge, Z. Ali-Adib, D. West, and T. King, “Efficient second-harmonic generation from thick all-polymeric Langmuir–Blodgett films,” Macromolecules 26, 1789–1792 (1993).
[CrossRef]

1992

M. Iwamoto, Y. Majima, F. Hirayama, M. Furuki, and L. S. Pu, “Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye,” Chem. Phys. Lett. 195, 45–49 (1992).
[CrossRef]

1991

G. J. Ashwell, E. J. C. Dawnay, A. P. Kuczynski, and P. J. Martin, “The highest observed second harmonic intensity from a multilayered Langmuir–Blodgett film structure,” in Physical Concepts of Materials for Novel Optoelectronic Device Applications. I. Materials Growth and Characterization, M. Razeghi, ed., Proc. SPIE 1361, 589–598 (1991).
[CrossRef]

1989

K. Y. Law and C. C. Chen, “Squaraine chemistry. Effect of orientation on the aggregation of surfactant squaraines in Langmuir–Blodgett films,” J. Phys. Chem. 93, 2533–2538 (1989).
[CrossRef]

1988

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

1986

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Ahmad, M. M.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Ali-Adib, Z.

P. Hodge, Z. Ali-Adib, D. West, and T. King, “Efficient second-harmonic generation from thick all-polymeric Langmuir–Blodgett films,” Macromolecules 26, 1789–1792 (1993).
[CrossRef]

Allen, S.

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

Ashwell, G. J.

G. J. Ashwell, G. M. S. Wong, D. G. Bucknall, G. S. Bahra, and C. R. Brown, “Neutron reflection from 2, 4-bis(4-(N-methyl-N-octylamino)phenyl)squaraine at the air–water interface and the linear and nonlinear optical properties of its Langmuir–Blodgett and spun-coated films,” Langmuir 13, 1629–1633 (1997).
[CrossRef]

G. J. Ashwell, “Centrosymmetric molecules for second harmonic generation,” Adv. Mater. 8, 248–250 (1996).
[CrossRef]

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

G. J. Ashwell, E. J. C. Dawnay, A. P. Kuczynski, and P. J. Martin, “The highest observed second harmonic intensity from a multilayered Langmuir–Blodgett film structure,” in Physical Concepts of Materials for Novel Optoelectronic Device Applications. I. Materials Growth and Characterization, M. Razeghi, ed., Proc. SPIE 1361, 589–598 (1991).
[CrossRef]

Bahra, G. S.

G. J. Ashwell, G. M. S. Wong, D. G. Bucknall, G. S. Bahra, and C. R. Brown, “Neutron reflection from 2, 4-bis(4-(N-methyl-N-octylamino)phenyl)squaraine at the air–water interface and the linear and nonlinear optical properties of its Langmuir–Blodgett and spun-coated films,” Langmuir 13, 1629–1633 (1997).
[CrossRef]

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

Bechgaard, K.

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

Bjørnholm, T.

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

T. Geisler and T. Bjørnholm, “Second harmonic generation from different types of Langmuir–Blodgett films,” Synth. Met. 55/57, 3842–3847 (1993).
[CrossRef]

Bothwell, B. D.

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

Brown, C. R.

G. J. Ashwell, G. M. S. Wong, D. G. Bucknall, G. S. Bahra, and C. R. Brown, “Neutron reflection from 2, 4-bis(4-(N-methyl-N-octylamino)phenyl)squaraine at the air–water interface and the linear and nonlinear optical properties of its Langmuir–Blodgett and spun-coated films,” Langmuir 13, 1629–1633 (1997).
[CrossRef]

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

Brunfeldt, K.

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

Bucknall, D. G.

G. J. Ashwell, G. M. S. Wong, D. G. Bucknall, G. S. Bahra, and C. R. Brown, “Neutron reflection from 2, 4-bis(4-(N-methyl-N-octylamino)phenyl)squaraine at the air–water interface and the linear and nonlinear optical properties of its Langmuir–Blodgett and spun-coated films,” Langmuir 13, 1629–1633 (1997).
[CrossRef]

Cade, N. A.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Chen, C. C.

K. Y. Law and C. C. Chen, “Squaraine chemistry. Effect of orientation on the aggregation of surfactant squaraines in Langmuir–Blodgett films,” J. Phys. Chem. 93, 2533–2538 (1989).
[CrossRef]

Chen, H. J.

H. J. Chen, K. Y. Law, and D. G. Whitten, “Aggregation of amphiphilic squaraines at the air–water interface and in Langmuir–Blodgett films,” J. Phys. Chem. 100, 5949–5955 (1996).
[CrossRef]

Dawnay, E. J. C.

G. J. Ashwell, E. J. C. Dawnay, A. P. Kuczynski, and P. J. Martin, “The highest observed second harmonic intensity from a multilayered Langmuir–Blodgett film structure,” in Physical Concepts of Materials for Novel Optoelectronic Device Applications. I. Materials Growth and Characterization, M. Razeghi, ed., Proc. SPIE 1361, 589–598 (1991).
[CrossRef]

Feast, W. J.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Furuki, M.

M. Iwamoto, Y. Majima, F. Hirayama, M. Furuki, and L. S. Pu, “Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye,” Chem. Phys. Lett. 195, 45–49 (1992).
[CrossRef]

Geisler, T.

T. Geisler and T. Bjørnholm, “Second harmonic generation from different types of Langmuir–Blodgett films,” Synth. Met. 55/57, 3842–3847 (1993).
[CrossRef]

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

Girling, I. R.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Gordon, P. F.

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

Hamilton, D. G.

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

Hirayama, F.

M. Iwamoto, Y. Majima, F. Hirayama, M. Furuki, and L. S. Pu, “Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye,” Chem. Phys. Lett. 195, 45–49 (1992).
[CrossRef]

Hodge, P.

P. Hodge, Z. Ali-Adib, D. West, and T. King, “Efficient second-harmonic generation from thick all-polymeric Langmuir–Blodgett films,” Macromolecules 26, 1789–1792 (1993).
[CrossRef]

Iwamoto, M.

M. Iwamoto, Y. Majima, F. Hirayama, M. Furuki, and L. S. Pu, “Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye,” Chem. Phys. Lett. 195, 45–49 (1992).
[CrossRef]

Jefferies, G.

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

Jørgensen, M.

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

Kennard, C. H. L.

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

King, T.

P. Hodge, Z. Ali-Adib, D. West, and T. King, “Efficient second-harmonic generation from thick all-polymeric Langmuir–Blodgett films,” Macromolecules 26, 1789–1792 (1993).
[CrossRef]

Kolinsky, P. V.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Kuczynski, A. P.

G. J. Ashwell, E. J. C. Dawnay, A. P. Kuczynski, and P. J. Martin, “The highest observed second harmonic intensity from a multilayered Langmuir–Blodgett film structure,” in Physical Concepts of Materials for Novel Optoelectronic Device Applications. I. Materials Growth and Characterization, M. Razeghi, ed., Proc. SPIE 1361, 589–598 (1991).
[CrossRef]

Larsen, J.

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

Law, K. Y.

H. J. Chen, K. Y. Law, and D. G. Whitten, “Aggregation of amphiphilic squaraines at the air–water interface and in Langmuir–Blodgett films,” J. Phys. Chem. 100, 5949–5955 (1996).
[CrossRef]

K. Y. Law and C. C. Chen, “Squaraine chemistry. Effect of orientation on the aggregation of surfactant squaraines in Langmuir–Blodgett films,” J. Phys. Chem. 93, 2533–2538 (1989).
[CrossRef]

Ledoux, I.

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

Lynch, D. E.

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

Majima, Y.

M. Iwamoto, Y. Majima, F. Hirayama, M. Furuki, and L. S. Pu, “Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye,” Chem. Phys. Lett. 195, 45–49 (1992).
[CrossRef]

Martin, P. J.

G. J. Ashwell, E. J. C. Dawnay, A. P. Kuczynski, and P. J. Martin, “The highest observed second harmonic intensity from a multilayered Langmuir–Blodgett film structure,” in Physical Concepts of Materials for Novel Optoelectronic Device Applications. I. Materials Growth and Characterization, M. Razeghi, ed., Proc. SPIE 1361, 589–598 (1991).
[CrossRef]

McLean, T. D.

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

Neal, D. B.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Peterson, I. R.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Petty, M. C.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Pu, L. S.

M. Iwamoto, Y. Majima, F. Hirayama, M. Furuki, and L. S. Pu, “Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye,” Chem. Phys. Lett. 195, 45–49 (1992).
[CrossRef]

Roberts, G. G.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

Roberts, M. P. S.

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

Robin, P.

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

Schaumburg, K.

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

West, D.

P. Hodge, Z. Ali-Adib, D. West, and T. King, “Efficient second-harmonic generation from thick all-polymeric Langmuir–Blodgett films,” Macromolecules 26, 1789–1792 (1993).
[CrossRef]

Whitten, D. G.

H. J. Chen, K. Y. Law, and D. G. Whitten, “Aggregation of amphiphilic squaraines at the air–water interface and in Langmuir–Blodgett films,” J. Phys. Chem. 100, 5949–5955 (1996).
[CrossRef]

Wong, G. M. S.

G. J. Ashwell, G. M. S. Wong, D. G. Bucknall, G. S. Bahra, and C. R. Brown, “Neutron reflection from 2, 4-bis(4-(N-methyl-N-octylamino)phenyl)squaraine at the air–water interface and the linear and nonlinear optical properties of its Langmuir–Blodgett and spun-coated films,” Langmuir 13, 1629–1633 (1997).
[CrossRef]

Adv. Mater.

G. J. Ashwell, “Centrosymmetric molecules for second harmonic generation,” Adv. Mater. 8, 248–250 (1996).
[CrossRef]

Chem. Phys. Lett.

M. Iwamoto, Y. Majima, F. Hirayama, M. Furuki, and L. S. Pu, “Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye,” Chem. Phys. Lett. 195, 45–49 (1992).
[CrossRef]

Electron. Lett.

D. B. Neal, M. C. Petty, G. G. Roberts, M. M. Ahmad, W. J. Feast, I. R. Girling, N. A. Cade, P. V. Kolinsky, and I. R. Peterson, “Second harmonic generation from LB superlattices containing two active components,” Electron. Lett. 22, 460–462 (1986).
[CrossRef]

J. Mater. Chem.

G. J. Ashwell, G. S. Bahra, C. R. Brown, D. G. Hamilton, C. H. L. Kennard, and D. E. Lynch, “2, 4-Bis(4-(N, N-dibutylamino)phenyl)squaraine: x-ray crystal structure of a centrosymmetric dye and the second-order nonlinear optical properties of its noncentrosymmetric Langmuir–Blodgett films,” J. Mater. Chem. 6, 23–26 (1996).
[CrossRef]

J. Phys. Chem.

H. J. Chen, K. Y. Law, and D. G. Whitten, “Aggregation of amphiphilic squaraines at the air–water interface and in Langmuir–Blodgett films,” J. Phys. Chem. 100, 5949–5955 (1996).
[CrossRef]

K. Y. Law and C. C. Chen, “Squaraine chemistry. Effect of orientation on the aggregation of surfactant squaraines in Langmuir–Blodgett films,” J. Phys. Chem. 93, 2533–2538 (1989).
[CrossRef]

Langmuir

G. J. Ashwell, G. M. S. Wong, D. G. Bucknall, G. S. Bahra, and C. R. Brown, “Neutron reflection from 2, 4-bis(4-(N-methyl-N-octylamino)phenyl)squaraine at the air–water interface and the linear and nonlinear optical properties of its Langmuir–Blodgett and spun-coated films,” Langmuir 13, 1629–1633 (1997).
[CrossRef]

Macromolecules

P. Hodge, Z. Ali-Adib, D. West, and T. King, “Efficient second-harmonic generation from thick all-polymeric Langmuir–Blodgett films,” Macromolecules 26, 1789–1792 (1993).
[CrossRef]

Nature (London)

G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra, and C. R. Brown, “Strong second harmonic generation from centrosymmetric dyes,” Nature (London) 375, 385–388 (1995).
[CrossRef]

Proc. SPIE

S. Allen, T. D. McLean, P. F. Gordon, B. D. Bothwell, P. Robin, and I. Ledoux, “Properties of polyenic Langmuir–Blodgett films,” in Nonlinear Optical Properties of Organic Materials, G. Khanarian, ed., Proc. SPIE 971, 206–215 (1988).
[CrossRef]

G. J. Ashwell, E. J. C. Dawnay, A. P. Kuczynski, and P. J. Martin, “The highest observed second harmonic intensity from a multilayered Langmuir–Blodgett film structure,” in Physical Concepts of Materials for Novel Optoelectronic Device Applications. I. Materials Growth and Characterization, M. Razeghi, ed., Proc. SPIE 1361, 589–598 (1991).
[CrossRef]

Synth. Met.

T. Bjørnholm, T. Geisler, J. Larsen, M. Jørgensen, K. Brunfeldt, K. Schaumburg, and K. Bechgaard, “Donor–acceptor interfaces in Langmuir–Blodgett films. Structural and optical features related to nonlinear optical properties,” Synth. Met. 55/57, 3813–3818 (1993).

T. Geisler and T. Bjørnholm, “Second harmonic generation from different types of Langmuir–Blodgett films,” Synth. Met. 55/57, 3842–3847 (1993).
[CrossRef]

Other

C. Bosshard, K. Sutter, P. Prêtre, J. Hulliger, M. Flörsheimer, P. Kaatz, and P. Günter, in Organic Nonlinear Optical Materials, A. F. Garito and F. Kajzar, eds., Vol. 1 of Advances in Optics (Gordon & Breach, Basel, 1995).

D. S. Chemla and J. Zyss, eds., Nonlinear Optical Properties of Organic Molecules and Crystals (Academic, Orlando, Fla., 1986).

G. J. Ashwell, G. Jefferies, N. D. Rees, P. A. Williamson, G. S. Bahra, and C. R. Brown, “Centrosymmetric chromophores: strong second harmonic generation from Langmuir–Blodgett films of hydroxy-substituted squaraines,” submitted to Langmuir.

S. Kim, M. Furuki, L. S. Pu, H. Nakahara, and K. Fukuda, “Unique monolayer assembly of squarylium dye with short alkyl chains,” J. Chem. Soc. Chem. Commun. 1201–1203 (1987).
[CrossRef]

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Figures (6)

Fig. 1
Fig. 1

Molecular structures: 2,4-bis[6-(N-butyl-2,3,4-trihydroquinoloyl)] squaraine (dye I); 2,4-bis[4-(N-methyl-N-hexylamino) phenyl]squaraine (dye II); 2,4-bis(9-julolidinyl)squaraine (dye III).

Fig. 2
Fig. 2

Molecular alignments: (a) SHG-active phase 1, (b) H-aggregate phase 2, (c) J-aggregate phase 3.

Fig. 3
Fig. 3

Surface pressure versus area (π–A) isotherm of dye I.

Fig. 4
Fig. 4

Visible spectra of Langmuir films of dye I at the air–water interface: π=0 mN m-1 (dotted curve) and π= 20 mN m-1 (solid curve). A progressive redshift of the absorption maxima occurs as the surface pressure increases from 0 to 20 mN m-1.

Fig. 5
Fig. 5

Visible spectrum of a LB monolayer of dye I deposited at 15 mN m-1. The spectra of films deposited at 520 mN m-1 are similar and have a broad absorption maximum at 730 nm.

Fig. 6
Fig. 6

Electrospray ionization mass spectrum of a dilute solution of dye I (2.2×10-5 mol dm-3) in a 4:1 mixture of CH3CN:H2O containing 0.1% formic acid. The mass peak at 457 corresponds to the monomer, whereas the peak at 913 corresponds to the dimeric aggregate.

Tables (1)

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Table 1 Analytical Data

Equations (2)

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CnH2n+1DπADπACnH2n+1.
CnH2n+1DπAσC6H4NH2O2NC6H4σDπACnH2n+1.

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