The Crystal Structure of a Squarylium Dye, 2,4-Bis(1,3,3-trimethyl-2-indolinylidenemethyl)cyclobutenediylium-1,3-diolate

Kobayashi, Yoshinori; Goto, Midori; Kurahashi, Mitsunori

doi:10.1246/bcsj.59.311

Cited by 33 publications

(16 citation statements)

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“…Roughly planar geometries were observed in NMR experiments by Dirk et al[21] as well as in crystal structures obtained by Kobayashi et al[29] In the case of conformation i of squaraine 3, semiempirical INDO/MRDCI calculations on the isolated molecule indicate that the conformation with a twist of 10 o is 0.12 eV higher in energy than the fully planar conformation, suggesting the existence of mostly planar structures.…”

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confidence: 80%

Electronic and Vibronic Contributions to Two‐Photon Absorption in Donor–Acceptor–Donor Squaraine Chromophores

Ohira

Rudra

Schmidt

et al. 2008

Chemistry A European J

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Many squaraines have been observed to exhibit two-photon absorption at transition energies close to those of the lowest energy one-photon electronic transitions. Here, the electronic and vibronic contributions to these low-energy two-photon absorptions are elucidated by performing correlated quantum-chemical calculations on model chromophores that differ in their terminal donor groups (diarylaminothienyl, indolenylidenemethyl, dimethylaminopolyenyl, or 4-(dimethylamino)phenylpolyenyl). For squaraines with diarylaminothienyl and dimethylaminopolyenyl donors and for the longer examples of 4-(dimethylamino)phenylpolyenyl donors, the calculated energies of the lowest two-photon active states approach those of the lowest energy one-photon active (1B(u)) states. This is consistent with the existence of purely electronic channels for low-energy two-photon absorption (TPA) in these types of chromophores. On the other hand, for all squaraines containing indolinylidenemethyl donors, the calculations indicate that there are no low-lying electronic states of appropriate symmetry for TPA. Actually, we find that the lowest energy TPA transitions can be explained through coupling of the one-photon absorption (OPA) active 1B(u) state with b(u) vibrational modes. Through implementation of Herzberg-Teller theory, we are able to identify the vibrational modes responsible for the low-energy TPA peak and to reproduce, at least qualitatively, the experimental TPA spectra of several squaraines of this type.

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confidence: 80%

Electronic and Vibronic Contributions to Two‐Photon Absorption in Donor–Acceptor–Donor Squaraine Chromophores

Ohira

Rudra

Schmidt

et al. 2008

Chemistry A European J

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“…The 1-alkyl derivatives of 2,4-bis(3,3-dimethylindolin-2-ylidenemethyl)cyclobutenediylio-1,3-diolate (InSq) have been studied for a variety of photophysical effects (for example, Kuramoto et al, 1989;Dirk & Kuzyk, 1990;Terpetschnig et al, 1993;Zhang et al, 1997). In several other studies of squaraine dyes, the only known crystal structure of an InSq derivative, InSq1 (Kobayashi et al, 1986), was cited and a discussion of molecular behaviour based on the non-planar conformation of this structure given. As part of a series of studies on the structural aspects of squaraine dyes, the 1-octyl derivative of InSq, InSq6, was prepared and the structure determined (Fig.…”

Section: S1 Commentmentioning

confidence: 99%

2,4-Bis(3,3-dimethyl-1-octylindolin-2-ylidenemethyl)cyclobutenediylio-1,3-diolate

Lynch

2002

Acta Cryst E

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“…This method is well developed in electrophotography. 15 The temperature of the sample was controlled by a heated nitrogen jet directed to the sample in a reservoir (9).…”

Section: Methodsmentioning

confidence: 99%

Second harmonic generation in polymers containing dithiosquarylium dye

et al. 1999

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Polymer layers containing the dye 2,4-bis(l,3,3-trimethyl-2-indolinylidenemethyl)-l,4-dithiosquaraine display second-order nonlinear optical properties. Depending on conditions of preparation of the layers, the monomer form of the dye or the intermolecular charge transfer complex between two dye molecules are responsible for the second harmonic generation.Key words: 2,4-his( 1,3,3-trimethyl-2-indoIinylidenemethyl)-1,4-dithiosquataine, poly(vinyl acetate), poly(vinyl ethylal), second harmonic generation, surface potential.Polymer compositions are materials on the basis of which transmission media, active optical elements, and devices for duplication of laser radiation frequencies compatible with modern microelectronic instruments can be developed.As known, ~-3 polarization (P(E)) of the medium occurs in the electric field of laser radiation E(ta), and donor-acceptor systems exhibit nonlinear effects:where X(I)E(t0), X(2)E2(r and X(3)E3(c0) are volume polarizations; and X(x), ~(2), and X(3) are polarizabilities of the first, second, and third orders, respectively. The ~(2) and X(3) values are also named hyperpolarizabilities of the first and second orders. When the E(ta) vector changes direction to -E(co), it can be obtain from Eq. (1) that in centrosymmetrical media, i.e., where P(+E) = -P(-E), the second-order susceptibility X(2) = 0. Molecules with intramolecular charge transfer and the structure of D--(g-conjugation system)--A (D is a donor and A is an acceptor group) are noncentrosymmetrical. As a result, the E(0~) field induces anharmonic polarization, and the radiation of oscillating dipoles can be presented by the sum of Fourier components with frequencies co, 2co, 3co, etc. The intensity (/) of the second harmonic (SH) measured experimentally is related to the susceptibility by the equation (2) where N is the number of donor-acceptor groups in the polymer unit volume; ](co) = [n2(0~) + 21/3 and J(2c0) = [n2(2r + 2]/3 are dimensionless coefficients relating the external electric field and the internal electric field acting upon the molecule (n(co) and n(2to) are refractive indices of laser radiation with the main and doubled frequencies, respectively); and 0 is the angle between the main axis of an individual molecule and perpendicular to the plane of the polymer layer. The molecular hyperpolarizability of the first order !-'4 is described by the equation (3) where e and m are the electron charge and mass, respectively; ~ = h/(2n) (h is Planck's constant); IF" is the difference of energies between the ground state of the donor-acceptor system u/0 = a~(D,A) + b~(D+A -) (a > b) and the charge transfer state ~(CT) = cu + dul(D+A -) (d > c); 6~t is the difference between the dipole moments of the chromophore molecule in the ground and excited states;f is the strength of the oscillator of the optical charge transfer transition (see, e.g., Ref. 5): f = 4.32-10-9EmaxAVl/2 (ema x is the maximum extinction coefficient, and AVv2/cm-I is the half-width of the charge transfer band); and hta and 2ho~ are the energies of...

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The Crystal Structure of a Squarylium Dye, 2,4-Bis(1,3,3-trimethyl-2-indolinylidenemethyl)cyclobutenediylium-1,3-diolate

Abstract: The crystal structure of 2,4-bis(1,3,3-trimethyl-2-indolinylidenemethyl)cyclobutenediylium-1,3-diolate has been determined. The space group is P21⁄c, with a=9.5115(4), b=15.712(1), c=15.174(1) Å, β=96.138(5)°, and Z=4. The molecule adopts the trans conformation.

Cited by 33 publications

References 2 publications

Electronic and Vibronic Contributions to Two‐Photon Absorption in Donor–Acceptor–Donor Squaraine Chromophores

Electronic and Vibronic Contributions to Two‐Photon Absorption in Donor–Acceptor–Donor Squaraine Chromophores

2,4-Bis(3,3-dimethyl-1-octylindolin-2-ylidenemethyl)cyclobutenediylio-1,3-diolate

Second harmonic generation in polymers containing dithiosquarylium dye

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