Supporting Information:

Triphenylamine derived 3-acetyl and 3-benzothiazolyl bis and tris coumarins:

Synthesis, photophysical and DFT assisted hyperpolarizability study

Yogesh Erandea, Shantaram Kothavale

a, Mavila C. Sreenath

b,

Subramaniyan Chitrambalamb, Isaac H. Joe*

b, Nagaiyan Sekar*

a

aDepartment of Dyestuff Technology, Institute of Chemical Technology

N. P. Marg, Matunga, Mumbai (MH) India-400019

Email: n.sekar@ictmumbai.edu.in, nethi.sekar@gmail.com

Tel.: +91 22 3361 1111/ 2707; Fax.: +91 22 3361 1020

bCentre for Molecular and Biophysics Research, Department of Physics,

Mar Ivanios College, Thiruananthapuram, Kerala, India-695015.

___________________________________________________________________________________

List of content:

FigS1: Absorption and emission plots for dyes 2, 3 and 4.

FigS2: Weller plots for dyes 1 to 4.

FigS3: Rettig plots for dyes 1 to 4.

Details of eq.6 from manuscript.

Rettig's equation for TICT.

NLO properties by spectroscopic method.

NLO properties by DFT method.

Z-scan equations.

Spectra.S1 –S12: 1H and

13C NMR spectras of compound 1 to 6.

Fig. S1: Absorption and emission plots for dye-2, 3 and 4.

Fig. S2: Weller plots for dye 1 to 4.

_________________________________________________________________________________________

Fig. S3: Rettig plots for dye 1 to 4.

Details of eq. 6 from manuscript:

𝜗 𝑎𝑏𝑠 − 𝜗 𝑒𝑚 =2(μ

e− μ

g)

2

𝑕𝑐𝑎3 𝜀 − 1

2𝜀 + 1−

𝑛2 − 1

2𝑛2 + 1 + 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (6)

where, 𝜗 ̅𝑎𝑏𝑠, and 𝜗 ̅𝑒𝑚 are wave numbers (cm-1

) of absorption and emission maxima respectively, 𝑕 is

the Planck’s constant (6.6256 X 10-27

erg), 𝑐 is the velocity of light (2.9979 X 1010

cm s-1

), (µe - µg)=

𝛥µeg is the difference between the charge transfer excited (S1) state and ground (S0) state dipole

moments. 𝑎 is the cavity radius in which the molecule resides (in cm; obtained by DFT from B3LYP/6-

31g(d) level volume calculations), 𝜀 is relative dielectric constant and 𝑛 is the refractive index of the

solvent.

Eq. 6 can be written as

𝑦 = 𝑚𝑥 + 𝑐

Where, 𝑦 = ῡ𝑎𝑏𝑠 − ῡ𝑒𝑚𝑠 , 𝑥 = 𝑓 𝜀,𝑛 = 𝜀−1

2𝜀+1−

𝑛2−1

2𝑛2+1 , 𝑚 =

2∆𝜇𝑒𝑔2

𝑕𝑐𝑎3

From the slope (m), the ∆𝜇𝑒𝑔was then derived.

Rettig's equation for TICT:

𝜗 𝑒𝑚 =2μ

e

2

𝑕𝑐𝑎3 𝜀 − 1

𝜀 + 2−

𝑛2 − 1

2𝑛2 + 4 + 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑆1)

NLO properties by spectroscopic method:

The charge transfer (CT) linear and non linear properties are calculated by solvatochromic method as

follow.

The linear polarizability (𝛼𝐶𝑇) expressed by the following reported equation1

𝛼𝐶𝑇 = 𝛼𝑥𝑥 = 2𝜇𝑒𝑔

2

𝐸𝑒𝑔 =

2𝜇𝑒𝑔2 𝜆𝑒𝑔

𝑕𝑐 (𝑆2)

where, x= direction of charge transfer, 𝑕 = Planks constant, c = velocity of light in vacuum,

𝜆𝑒𝑔=The wavelength of transition from the ground state to excited state, μeg is the transition dipole

moment, related to the oscillator strength f. Values of 𝜇𝑔𝑒 is transition dipole moment and 𝐸𝑔𝑒 energy of

ground to excited state charge transfer transition and can be obtained by standard spectroscopic methods2

The first order hyperpolarizability (𝛽𝐶𝑇/𝛽xxx) is determined using Oudar two level microscopic

model by using the equation-S334

𝛽𝐶𝑇 = 𝛽𝑥𝑥𝑥 =3𝜇𝑔𝑒

2

2𝐸𝑔𝑒2 ∆𝜇𝑔𝑒 (S3)

The experimental results on the emssion solvatochromism allowed information on the difference

between the excited ICT and ground state dipole moments ∆𝜇𝑒𝑔 = 𝜇𝑒 − 𝜇𝑔 to be obtained by using

Lippert -Mataga theory5.

The “solvatochromic descriptor” for the third order hyperpolarizability (γxxxx) or (γSD) can be obtained

by following equation6.

𝛾𝑆𝐷 = 𝛾𝑥𝑥𝑥𝑥 ∝1

𝐸𝑔𝑒3 𝜇𝑔𝑒

2 ∆𝜇𝑒𝑔2 − 𝜇𝑔𝑒

2 (𝑆4)

NLO properties by theoretical method:

The total static dipole moment μ is expressed by following equation

𝜇 = 𝜇𝑥2 + 𝜇𝑦2 + 𝜇𝑧2 (S5)

The isotropic polarizability can be calculated from the trace of the polarization tensor,

𝛼0 = 𝛼𝑥𝑥 +𝛼𝑦𝑦 +𝛼𝑧𝑧

3 (𝑆6)

Anisotropy of the polarizability Δα is expressed by

∆𝛼 = 2−1 2 𝛼𝑥𝑥 + 𝛼𝑦𝑦 2

+ 𝛼𝑧𝑧 + 𝛼𝑥𝑥 2 + 6𝛼𝑥𝑥

2 (𝑆7)

The mean / static first hyperpolarizability (β0) is expressed by

𝛽0 = 𝛽𝑥2 + 𝛽𝑦

2 + 𝛽𝑧2

1 2 (𝑆8)

𝛽0 = (𝛽𝑥𝑥𝑥 + 𝛽𝑥𝑦𝑦 + 𝛽𝑥𝑧𝑧 )2 + (𝛽𝑦𝑥𝑥 + 𝛽𝑦𝑦𝑦 + 𝛽𝑦𝑧𝑧 )2 + (𝛽𝑧𝑥𝑥 + 𝛽𝑧𝑦𝑦 + 𝛽𝑧𝑧𝑧 )2 1

2 (𝑆9)

Where, βx, βy, and βz are the components of the second-order polarizability tensor along the x, y, and

z axes

The mean second hyperpolarizability (𝛾) is expressed by

𝛾 =1

5 𝛾𝑥𝑥𝑥𝑥 + 𝛾𝑦𝑦𝑦𝑦 + 𝛾𝑧𝑧𝑧𝑧 + 2 𝛾𝑥𝑥𝑦𝑦 + 𝛾𝑦𝑦𝑧𝑧 + 𝛾𝑧𝑧𝑥𝑥 (𝑆10)

Z-scan equations:

For the open aperture measurement, the normalized transmittance as a function of position along

the z axis can be represented as

𝑇 𝑧, S = 1 = −𝑞0 𝑧, 0 𝑚

(𝑚 + 1)3/2

∞

𝑚=0

for 𝑞0 < 1 (𝑆11)

where q0(z,0) = βI0(t)Leff and Leff = (1–e-αl

)/α is the effective thickness with the linear absorption

coefficient α, I0 is the irradiance at the focus.

For closed aperture the transmittance and nonlinear refractive index n2 are obtained by following

equations,

𝑇 𝑧,∆ϕ0 = 1 −4∆ϕ0𝑥

𝑥2 + 9 𝑥2 + 1 𝑆12

n2 =∆ϕ0 𝜆

2πI0Leff (𝑆13)

Where ∆ϕ0 a phase shift and λ is is the wavelength of laser used.

The real (Reχ(3)) and imaginary (Imχ(3)) part of the third-order susceptibility χ(3)

of the sample can be

calculated by the following equations.

χRe(3)

= 10−4ε0n0

2c2

πn2 (𝑆14)

χIm(3)

= 10−2ε0n0

2c2λ

4π2𝛽 (𝑆15)

where, ε0 is the permittivity of free space, no is the linear refractive index and c is the velocity of

light in vacuum.

References:

1 F. Momicchioli, G. Ponterini and D. Vanossi, J. Phys. Chem. A, 2008, 112, 11861–11872.

2 B. J. Coe, J. A. Harris, I. Asselberghs, K. Clays, G. Olbrechts, A. Persoons, J. T. Hupp, R. C.

Johnson, S. J. Coles, M. B. Hursthouse and K. Nakatani, Adv. Funct. Mater., 2002, 12, 110–116.

3 J. L. Oudar and D. S. Chemla, J. Chem. Phys., 1977, 66, 2664–2668.

4 A. B. Tathe and N. Sekar, Opt. Mater. (Amst)., 2016, 51, 121–127.

5 E. Lippert, Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft für Phys. Chemie,

1957, 61, 962–975.

6 M. G. Kuzyk and C. W. Dirk, Phys. Rev. A, 1990, 41, 5098–5109.

1H NMR Dye-1:

Spectra.S1 - 1

H NMR (CDCl3, 500 MHz) spectrum of Dye-1.

13C NMR Dye-1:

Spectra.S2 - 13

C NMR (CDCl3, 125 MHz) spectrum of Dye-1.

1H NMR Dye-2:

Spectra.S3- 1

H NMR (CDCl3, 500 MHz) spectrum of Dye-2.

13C NMR Dye-2:

Spectra.S4 - 13

C NMR (CDCl3, 125 MHz) spectrum of Dye-2.

1H NMR Dye-3:

Spectra.S5- 1

H NMR (CDCl3, 500 MHz) spectrum of Dye-3.

13C NMR Dye-3:

Spectra.S6 - 13

C NMR (CDCl3, 125 MHz) spectrum of Dye-3.

1H NMR Dye-4:

Spectra.S7 - 1

H NMR (CDCl3, 500 MHz) spectrum of Dye-4.

13C NMR Dye-4:

Spectra.S8 - 13

C NMR (CDCl3, 125 MHz) spectrum of Dye-4.

1H NMR Comp-5:

Spectra.S9 - 1

H NMR (CDCl3, 500 MHz) spectrum of Comp-5.

13C NMR Comp-5:

Spectra.S10 - 13

C NMR (CDCl3, 125 MHz) spectrum of Comp-5.

1H NMR Comp-6:

Spectra.S11 - 1

H NMR (CDCl3, 500 MHz) spectrum of Comp-6.

13C NMR Comp-6:

Spectra.S12 - 13

C NMR (CDCl3, 125 MHz) spectrum of Comp-6.