Gugu Rutherford Conjugated Dyes

Abstract:
A study of polymethine dyes was done using a spectrophotometer in

order to obtain spectra that analyze NO THEY DON’T YOU DO THATthe

excited energy states and the effects of the polymethine chain on the

molecular structure. The spectrophotometer observed AN INSTRUMEN

CANNOT OBSEVE ANYTHINGMONLY THE EXPERIMENTER DOESa maximum

wavelength, λmax, for 1,1-diethyl-2,2-cyanine iodide,DCI, to be indicated at

522 nm. Data for the λmax for 1,1-diethyl-2,2-carbocyanine iodide, PCI, was

determined OK to be 563 nm. While the λmax for 1,1-diethyl-2,2-

dicarbocyanine iodide, DDI, was determined to be 692 nm. Results for the

polymethine dyes where all reported to be within a reasonable range once

compared to the literary values. Theoretical values for the λmax were also

calculated. All the experimental values produced values closer to the literary

values than the theoretical values. Literary values for λ max were 524 nm

for DCI, 606 nm for PCI, and 707 nm for DDI.

THE REAL QUESTION IS HOW WELL THE EXPERIMENTAL VALUES AGREE WITH

THE PARTICLE IN A BOX MODEL

Introduction:
Polymethine dyes can be essential tools in further analyzingTHE DYES

DON’T ANALYZE ANYTHING the free electron model. The main reason it is

important to analyze the free electron model is so that there is a better

understanding of energy transition states as molecules interact. A

polymethine dye consist of two heterocyclic ring systems linked by an

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Gugu Rutherford Conjugated Dyes

unsaturated aliphatic chain, and this structure can be symmetric or

asymmetric(Treadwell, 1979). What makes the polymethine dye ideal for

analyzing the free model is that it is known for having an ideal excited

state(Treadwell, 1979). In order for this excited state to be ideal several

conditions must be met, and the conditions are that the molecular structure

must be set up in a way to reduce steric hindrance within the

molecule(Treadwell, 1979). Polymethine dyes meet this requirement

because its structure is set up to where the length of its polymethine chain

tends to reduce steric hindrance(Treadwell, 1979).

Another advantage that polymethine dyes have that makes them ideal

to observe energy transitions is there heterocyclic rings. These heterocyclic

rings have the ability to twist so that the polymethine chain enhances the

rate of internal conversion of the ground state(Treadwell, 1979). For a

molecule to do this is a rare quality. Usually there is a loss of energy due to

intermolecular vibration and rotation that makes it difficult for a molecule to

go back to its ground state (Treadwell, 1979).

During this experiment the main objective is to focus on obtain

maximum wavelengths from the experimental recordings and the calculated

theoretical maximum wavelength. The theoretical maximum wavelength will

be obtained using the following equation.

λmaxtheoretical=63.7 (p+3+α)2p+4 Equation 1

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Gugu Rutherford Conjugated Dyes

In order for the spectrophotometer to pick up an absorbance and wavelength

reading the molecule must exhibit resonance(Treadwell, 1979). What occurs

is a resonance delocalization in which as the electron density increases

because of the polymethine chain then so does the absorption intensity and

wavelength(Treadwell, 1979). The maximum wavelength becomes

distinguishable from the rest of the wavelengths because at this time there

is a bathochromic shift(Treadwell, 1979). Bathochromic shifts occur because

there is a change in the molecular environment that causes the spectra

band position to switch to a longer wavelength. In the polymethine dye this

is occurring because the conjugated system is lengthening at this time

causing an increase in absorbance and an increase in length of the

polymethine chain(Treadwell, 1979).

Results:
Solutions of DCI, PCI, and DDI where prepared in methanol as a

solvent. The concentration of each solution was approximately 10-3 M.

Each solution was then analyzed using the spectrophotometer. NOW YOU’VE

GOT IT Data obtained from the spectrophotometer was the absorbance band

location and the wavelength that the absorbance occurred at. This

information is included in Table 1,2, and 3. In the data set there is a

maximum wavelength , and in order to better gauge the ideal location of the

maximum wavelength a series of calculations were done to find a theoretical

maximum wavelength. Results for the theoretical wavelength are located in

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Gugu Rutherford Conjugated Dyes

Table 4. Figure 1, 2, and 3 include the graphs of the absorbance versus the

wavelength for each solution.

Table 1: Sample peaks and absorbance of

1,1-Diethyl-2,2-Cyanine Iodide(DCI)
Sample Peaks Absorbance

227 nm 1.5760 AU

490 nm 1.7841 AU

522 nm 2.4379 AU

Table 1

Table 2: Sample peaks and absorbance of

1,1-Diethyl-2,2-Carbocyanine Iodide(PCI)
Sample Peaks Absorbance

236 nm 1.2449 AU

217 nm 1.2709 AU

563 nm 2.7611 AU

Table 2

Table 3: Sample peaks and absorbance of

1,1-Diethyl-2,2-Dicarbocyanine Iodide (DDI)

Sample Peaks Absorbance

324 nm 0.6309 AU

692 nm 0.9888 AU

238 nm 1.7310 AU

Table 3

Solution λmax Theoretical

1,1-Diethyl-2,2-Cyanine Iodide 437.15 nm

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Gugu Rutherford Conjugated Dyes

1,1-Diethyl-2,2-Carbocyanine Iodide 564.54 nm

1,1-Diethyl-2,2-Dicarbocyanine Iodide 691.93 nm

Table 4WHY NOT PLACE THE EXPERIMENTALLY DETERMINED VALUES AND THE
EXPERIMENTAL ONES IN THE SAME TABLE

Figure 1 Absorbance of DCI versus the wave length, λ

DO NOT NEED TO GRAPH ABSORBANCE

Figure 2 Absorbance of PCCI versus the wave length, λ

Figure 3 Absorbance of DDI versus the wavelength, λ

Discussion:
According to Table 1 the experimental value for the maximum

wavelength for DCI was analyzed to be 522 nm at an absorbance of 2.4379

AU. While Table 2 reported that PCI had a maximum wave length of 563 nm

at an absorbance of 2.7611AU. Table 3 results concluded that for DDI the

maximum wave length was 692 nm at an absorbance of 0.9888AU. Literary

values for the maximum wave lengths indicated that DCI should have a

λmax of 524 nm, PCI should have a λmax of 606 nm, and DDI should have a

λmax of 707 nm (Brian O’Regan, 1995). The values for the DCI and DDI are

very similar to the literary values. However, the PCI values are off slightly

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Gugu Rutherford Conjugated Dyes

from the literary values. PCI maybe off from the literary value because of

the fact that the PCI in the experiment was analyzed in methanol as a

solvent while the literary value was analyzed in ethanol as a solvent. The

solvent that is used has a role in the absorption band read and λmax

obtained, because the solvent plays a major role in the rate of the

extraction process of the polymethine dye while it is being analyzed in the

spectrophotometer(P. Kumar, 2010).

Calculations for the theoretical maximum wave length were done using

equation 1. The results for these theoretical maximum wave length values

are indicated by Table 4 as being 437.15 nm for DCI, 564.54 nm for PCI, and

691.93 nm for DDI. PCI and DDI were the polymethine dyes that had

theoretical values in agreement with both the literature and the

experimental values. However, the DCI had a theoretical value that was very

low compared to the experimental and literature. It is important to note the

reason for these value differences are that the theoretical values are

representative of the excited states of energy and are not representative of

the ground state so these values are normally less accurate.

The main reason for determining the λ max is to analyze how the free

electron model can change as the length of the polymethine chain

increases(Treadwell, 1979). Essentially what is occurring is that as the

polymethine chain increases then so does the absorbance

intensity(Treadwell, 1979). All the experimental, literary, and theoretical

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Gugu Rutherford Conjugated Dyes

values indicate this observation to be true because the polymethine dye

with the longest polymethine chain was DDI and it had the highest value for

λ max.

Figures 1, 2, and 3 all indicate there is a linear relationship with the

absorbance and the wave length. However, Figure 1 and Figure two both

illustrate on their graph that as the absorbance increased so did the wave

lengths of the peaks creating a positive slope. While Figure 3 show that as

the absorbance decreased the wave length increased, so this created a

negative slope. To explain why this trend was prevalent in the data set; it is

important to understand the effect of large molecular groups being present

in a polymethine chain or the heterocyclic ring system, and their affect on

the bathochromic shift(Treadwell, 1979). The bathochromic shifts affect the

absorption spectrum by changing the absorption to a longer wave length,

but due to the large molecular groups being present this leads to an increase

in steric hindrance(Treadwell, 1979). Normally the bathochromic shift will

cause the conjugated system to lengthen which leads to an increase in

absorbance intensity, but with the increase in steric hindrance this lead to a

decrease in absorbance intensity(Treadwell, 1979). The decrease in

absorbance intensity is why Figure 3 has the graph of DDI versus the wave

length having a negative slope, and this is reasonable considering that

structurally DDI has the largest groups on its polymethine chain of the

polymethine dyes that were analyzed(Treadwell, 1979). The larger the

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Gugu Rutherford Conjugated Dyes

groups are on the polymethine chain increases the electron density;

therefore, leading to an increase in steric hindrance(Treadwell, 1979).

Polymethine dyes allowed for there to be a more solid understanding

of the energy transition states, and also it lead a better understanding of

the effects that molecular structure have on the ability to attain excited and

ground state energy levels. The data obtained while observing the

polymethine dyes in the spectrophotometer also helps to establish these

relationships by looking at the effects of polymethine chains and heterocyclic

ring systems on the spectra. If possible it would be helpful to further analyze

the solvent choice on the spectra by having future experiments with several

solvents being used to compare measurements of the polymethine dyes in

the spectrophotometer.

Works Cited
1. PICOSECOND TIME RESOLVED FLUORESCENCE LIFETIMES. Treadwell, C.J. and
Keary, C.M. London : North Holland Publishing Company, April 4, 1979, Journal of
Chemical Physics, Vol. 43, pp. 307-316.

2. Efficient Photo-Hole Injection from Absorbed Cyanine Dyes into Electrodepositied

Copper(1)Thiocyanate Thin Films. Brian O’Regan, Brian and Schwartz, Daniel
T. Seattle : University of Washington, 1995, Chemical Matter, Vol. 7, pp. 1349-1354.

3. Solvent Extraction and Spectrophotometric Determination of Pigments of Some

Algal Species from the Shore of Puthumadam, Southeast Coast of India. P. Kumar,
P., Ramakritinan, C.M. and Kumaraguru, A.K. 1, Madurai : Research India
Publications, 2010, International Journal of Oceans and Oceanography, Vol. 4, pp.
29-34. ISSN 0973-2667.

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