A REPORT ON

Synthesis of Panchromatic Aza-BODIPYs for Light Harvesting Applications

Submitted in partial fulfilment of the requirements

of the degree of

Masters of Science (Analytical Chemistry)

by

ASHISH
ROLL NO. 196952

Under the Guidance

of
Dr. Raghu Chitta
Assistant Professor
Department of Chemistry

DEPARTMENT OF CHEMISTRY
National Institute Of Technology
Warangal-590018

May 13, 2021

 ABSTRACT

Large conjugated organic dyes have found applications in biological labelling and analytical diagnos-
tic tests. Boron-dipyrromethene (BODIPY) is one such class of organic fluorescent dyes that have a
wide range of photo harvesting applications. BODIPY has a rigid structure and hence high fluores-
cence yields from the dipyrromethene boron framework. Further it is possible to increase the spectral
performance, molar extinction coefficients and fluorescence yields by using derivatives of BODIPY
like Aza-boron-dipyrromethene (Aza-BODIPY). Synthetic pathways have and the Jablonski diagram
depicting the photophysical characteristics of the aza bodipy dyes have been studied. The strong
NIR absorption, versatile structure for functional engineering, and tunable spectroscopic properties
of aza bodipy make it an ideal choice for photo-harvesting in DSSC. A research problem comprised
of the synthesis of panchromatic Aza-BODIPY dyes for their applications as photo-harvesting de-
vices has been chosen and the related literature has been thoroughly reviewed. In the regard to the
synthesis of the panchromatic Aza-BODIPYs,functionalized with triphenylamine and naphthalene
chromophores and its precursors, chalcone and nitro have been synthesized and fully characterized
using 1H NMR and ESI-MS studies.

2
 CERTIFICATE

I hereby certify that the work on “Synthesis of Panchromatic Aza-BODIPYs for Light
Harvesting Applications” is the bonafide record of the seminar successfully completed as a part
of academic curriculum of NIT Warangal by Ashish (Roll No. 196952) under my supervision in
M.Sc. Chemistry (Analytical Chemistry ), Semester IV, Department of Chemistry.

Dr. Raghu Chitta

Assistant Professor
Department of Chemistry

3
 DECLARATION

I declare that this written submission represents my ideas in my own words and where others
ideas or words have been included, I have adequately cited and referenced the original sources. I
also declare that I adhered to all the principles of academic honesty and integrity and have not
misrepresented or fabricated or falsified any idea /data /fact /source in my submission. I understand
that any violation of the above will be cause for disciplinary action by the institute and can also
evoke penal action from the sources which have thus not been properly cited or from whom proper
permission has not been taken when needed.

Ashish
Roll No: 196952
Date: May 13, 2021

4
 ACKNOWLEGEMENT

I owe my profound gratitude to my guide, Dr. Raghu Chitta (Assistant Professor), Department
of Chemistry, NIT Warangal for giving constant encouragement and guidance in writing this seminar
report. Under his tutelage, I was able to complete this on time.
I am thankful to Dr. Vishnu Shanker, Head, Department of Chemistry for his keen interest and
encouragement rendered during the course of this work. Their suggestions and instructions have
served as the major contribution towards the completion of this report. I would also like to thank
all my teachers who have taught me the basics of Analytical Chemistry and helped me in guiding
during the process.
Finally, I wish to express my thanks to my beloved parents for their support and encouragement
throughout my work.

Ashish
Roll No: 196952
Date: May 13, 2021

5
Contents

DECLARATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

1 Introduction 8

2 The solar cell 9

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2 Working Principal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3 The Generations of the Solar cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.1 First Generation Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.2 Second Generation Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.3 Third Generation Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3 Dye-sensitized solar cell 13

4 Aza-BODIPY as DSSC dye 15

4.1 Aza-BODIPY based panchromatic dyes . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.2 What is BODIPY Dyes ? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.3 Aza-Borondipyrromethenes and its synthesis . . . . . . . . . . . . . . . . . . . . . . . 18
4.4 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.4.1 Synthesis Details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.4.2 Synthesis of TNCHAL (tolyl napthalene chalcone) . . . . . . . . . . . . . . . . 19
4.4.3 Synthesis of TNNO2 (tolyl napthalene nitro) . . . . . . . . . . . . . . . . . . . 20
4.4.4 Synthesis of TNAZDPM(tolyl napthalene Azaboron dipyrromethene) . . . . . 21
4.4.5 Synthesis of TNBAZDPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

6
List of Figures

2.1 Construction of solar cell[1] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.2 Mono and poly christaline Solar cell[2] . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3 Cost of solar cell accordening with the generation[3] . . . . . . . . . . . . . . . . . . . 12

3.1 Dye-sensitized solar cell device schematic . . . . . . . . . . . . . . . . . . . . . . . . . 14

3.2 Dye-sensitized solar cell device working . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4.1 Whole Energy Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

4.2 Aza-Borondipyrromethenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.3 Basic types of cyanine structure [4] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.4 Numbering scheme used for the Bodipy framework derived from indacene [4] . . . . . 17
4.5 Aza-Borondipyrromethenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.6 Synthetic pathway of preparation of TNAZDPM . . . . . . . . . . . . . . . . . . . . . 19
4.7 Preparation pathway of TNCHAL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.8 NMR of TNCHAL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.9 Synthatic Pathway of TNNO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.10 NMR spectra of TNNO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.11 Preparation of TNAZDPM from TNNO2 . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.12 Mass Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.13 Mass spectra of TNAZADPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.14 Synthetic pathway of preparation of TNBAZDPM . . . . . . . . . . . . . . . . . . . . 25
4.15 Mass spectra of TNBAZDPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.16 NMR of TNBAZDPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.17 Absorbance Spectra of TNBAZDPM . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

7
Chapter 1

Introduction

The use of fluorescent dyes have been of interest to organic chemists since, their use is versatile and
has applications spanning diverse fields. One of their applications of prime importance is for labelling
compounds to easily detect them using a plethora of spectroscopic techniques available today. Mostly,
the efficiency of solar energy capture depends on the absorption properties of sensitizer employed.
Hence, the absorption spectrum of a sensitizer plays an important role in determining the conver-
sion efficiency of a DSSC[5]. Many organometallic sensitizers including ruthenium(II) polypyridyl
complexes such as N3, N719 and cationic cyclometalated iridium complexes[6] have been extensively
used as sensitizers in DSSC and overall efficiencies ranging from 10-12 % have been achieved. These
dyes are photo-stable and robust to the environment of the solar cell fabrication. However, the major
technical disadvantages with the systems are that the metal complexes are expensive due to rarity of
the metal, tedious purification process and lower molar absorptivity values in the red region of the
visible spectrum, where the light harvesting process is maximum.
In order to overcome the above difficulties, expensive metal sensitizers have been substituted by
metal free sensitizers[7]. Among these, porphyrins[8],phthalocyanines[9], boron dipyrromethenes[10]
are found to be probable alternative sensitizers based on their outstanding thermal, electronic and
photoelectrochemical properties. Even though the metal free organic dyes, in terms of cost, prepa-
ration and physical properties, have served as the potent substitutes for organometallic sensitizers in
DSSCs, the apparent downfall of these metal free organic sensitizers is their narrow spectral band-
widths which have limited their applications for commercial purposes. Hence, one of the key steps
to improve the efficiencies of DSSCs relies on increasing their absorption cross section using multiple
dyes. Additionally, as the increase in the rate of charge separation and decrease in the rate of charge
recombination determines the efficiency of the DSSC, incorporation of secondary electron donors in
the chromophore system would improve the efficiency of DSSC.

8
Chapter 2

The solar cell

2.1 Introduction
The solar cell is a device that converts the energy of the sunlight into electric energy. It is a physical
and chemical process. The solar cell is a just type of the PN-junction diode. The combo of cells is
known as the solar panel. A normal voltage given by the solar cell is 0.5 to 0.6 volts. This amount
of electric energy only in the case of one solar cell. When we connect no. of cells in a solar panel at
that time we can get a considerable amount of electric energy, this energy is sufficient to do all types
of work. The construction of the solar cell is nearly the same as the PN junction diode, but in this
p-type layer is very thin as compared to the n-type layer. the whole setup is placed on a glass plate.
We also connect a current collecting voltage to the n-type, which collects electrons from the p-type
and sends it to the p-type through the external circuit. As it is shown in the figure 2.1.

Figure 2.1: Construction of solar cell[1]

9
2.2 Working Principal
When a photovoltaic cell is placed in the sunlight or in front of a light source, electron-hole pairs
get displaced. In the n-type side, an electron is created, and on the other hand, on the p-side, the
hole starts producing. This electron can move towards the p-side and hole towards the n-side but
with the passage of time, it will not be possible because of the formation of the depletion layer. This
barrier cannot be crossed by the electron and holes unless potential is externally applied. In reality,
their recombination of electrons and holes occurs in the junction to form what is known as EHPs or
Electron Hole Pairs. When photons of suitable energy reach the junction, they are able to excitethe
electrons and cause the separation of the charge carriers, hence generating a voltage. With more
and more collection of the charged particles on each side of the junction, and more voltage being
generated, it acts as a cell. We can connect the load and collect electric energy. The solar energy
lasts for a long time, is nature-friendly, and is low maintenance. The disadvantages would be the
high price of installation and the lack of sunlight during the night and cold seasons. As it is shown
in Figure 2.1.

2.3 The Generations of the Solar cell

There are different generations of solar cells based on different criteria. The first generation of solar
cells is those which have low efficiency but high cost. Second generation solar cells are those which
have even low frequency but they are comparatively cheaper than the first generation solar cells.
But due to the low cost, the second generation solar cells are much more affordable than the first
generation solar cells. Third generation solar cells are those which have a low cost but high efficiency
but this technology is used only on research-level and not on commercial basis. A high number of
research is going on in this area. So let’s discuss the different generations of solar cells.

2.3.1 First Generation Solar Cells

The first generation of solar cells can be divided into two broad classes. The first one is Monocrys-
talline Si Solar Cells. They are expensive owing to the high energy, and thereby high cost to manufac-
ture a highly ordered single crystal. Wafers are usually made out of them, and being a single crystal
the efficiency is also high; in fact, one of the highest efficiencies of first generation solar cells(around
24%) is that of Monocrystalline Solar cells. Each wafer has a capacity of 2 to 4 watts. That’s why
we use them in a panel which produces a considerable amount of electricity. A cheaper alternative
is the Polycrystalline Si Solar Cells, which although is slightly lower in efficiency(around 19%) but
also is more economical fact and advices[11]. Mono and ploy crystal solar cells shown in figure .

10
 Figure 2.2: Mono and poly christaline Solar cell[2]

2.3.2 Second Generation Solar Cells

The third type is basically Thin-film Solar Cells.In many cases, it is just amorphous Si solar cells.
Si crystals are not made here, and amorphous Si is deposited onto a substrate, which may be glass,
plastic, etc. to form a thin film. Since Si is not crystallized, there is a lower energy expenditure
making it cheap but also given the randomness that an amorphous material brings; the efficiency is
lower(around 10%). The huge advantage of amorphous Si solar cells is that they are flexible and of
great use for portable applications.
Since only a thin-film of the active material is required, it needs less amount of the material, thereby
significantly bringing down the cost. As compared to the thickness of a wafer of Si in the first
generation, which is about a few hundred m, the thickness of the material deposited on the substrate
is only a few tens of nm thick. There is also no need for metallic fingers in thin-film solar cells, and
thus a larger area can be illuminated and also can be used in applications such as cars and buildings
easily. Another example of a thin-film solar cell is Copper Indium Gallium Selenide(CIGS) Solar cell
and Cadmium Telluride Solar cell(CdTe). The efficiency, as well as the cost of the Second generation
solar cells, is less than that of the first generation cells. This thin-film can be folded into the needed
structure as an advantage of the thin-film solar cell.

2.3.3 Third Generation Solar Cells

The third generation is the type of photovoltaic cell, which has a high level of efficiency and low
cost. It is all done by maintaining environmental and economic conditions and the efficiency of the
third-generation solar cell is increased. This efficiency can be increased by the devices by avoiding the
Shockley-Queisser limit for single-bandgap which fixes the efficiency of a solar cell. The efficiency may
fluctuate between 31 to 41 percent depending on the concentration ratio. There are two problems
while doing this, first is increasing the absorption power of a cell in low light and second is increasing
the energy of a photon to pass the energy bandgap. Light can be concentrated on a solar cell to
increase overall efficiency. The solar radiation of the sun is concentrated on a fixed point and it falls
on the small semiconductor photovoltaic device. It is essential to have a good reflection system. To
increase efficiency, multiple energy stages are required, which absorb light efficiently from a broader

11
 Figure 2.3: Cost of solar cell accordening with the generation[3]

spectrum. The efficiency and cost of a solar cell of different generations shown in figure 2.3. Metal
halide Perovskite Solar cells have a unique feature that they can absorb light from the different
spectrums of light and produce charge carriers efficiently. We will discuss more perovskite solar cells
in the next chapter Conibeer and Willoughby[12] .

12
Chapter 3

Dye-sensitized solar cell

referred to as dye sensitised cells (DSC), are a third generation photovoltaic (solar) cell that converts
any visible light into electrical energy.This new class of advanced solar cell can be likened to artificial
photosynthesis due to the way in which it mimics nature’s absorption of light energy. Dye Sensitized
solar cells (DSSC) were invented in 1991 by Professor Michael Graetzel and Dr Brian O’Regan
at École Polytechnique Fédérale de Lausanne (EPFL), Switzerland and is often referred to as the
Gräetzel cell, we call it G Cell[13]. DSSC is a disruptive technology that can be used to produce
electricity in a wide range of light conditions, indoors and outdoors, enabling the user to convert both
artificial and natural light into energy to power a broad range of electronic devices. A dye-sensitized
solar cell (DSSC, DSC or DYSC[14]) is a low-cost solar cell belonging to the group of thin film solar
cells.[15] It is based on a semiconductor formed between a photo-sensitized anode and an electrolyte,
a photo electrochemical system. The DSSC has a number of attractive features; it is simple to
make using conventional roll-printing techniques, is semi-flexible and semitransparent which offers a
variety of uses not applicable to glass-based systems, and most of the materials used are lowcost. In
practice it has proven difficult to eliminate a number of expensive materials, notably platinum and
ruthenium, and the liquid electrolyte presents a serious challenge to making a cell suitable for use in
all weather.A typical DSSC is shown in figure 3.1 and 3.2. In next chapter we will discuss about
Aza-BODIPY dye which can be used in DSSC to harvest electrical energy.

13
Figure 3.1: Dye-sensitized solar cell device schematic

Figure 3.2: Dye-sensitized solar cell device working

14
Chapter 4

Aza-BODIPY as DSSC dye

4.1 Aza-BODIPY based panchromatic dyes

Among the NIR dyes, well-known dyes are merocyanine[13],phthalocyanines[16, 17],and diketopy-
rrolopyrroles Recently Aza-BODIPYs have been emerged as promising dyes due to high stability, high
solubility, their facile synthesis, and abnormal photophysical properties with high molar coefficient
values (1 × 105M −1 cm− 1) and high fluorescence quantum yields in the NIRregion. Aza-BODIPYs
also have promising applications in biology such as photosensitizers in photodynamic therapy[18], as
fluorescent probes for biological imaging,16 and as laser dyes. The photosensitizers with NIR region
absorption and emission properties have received more attention in biological applications such as
cell recognition and in vivo imaging, since the property of deep penetration into biological tissues
is favorable by NIR emission.The Aza-BODIPY-zinc phthalocyanines and Aza-BODIPY-fullerene
supramolecular systems have been successfully synthesized and systematically investigated for the
electron transfer process. Owing to the exceptional optical properties of the Aza-BODIPY deriva-
tives, they have been studied for applications in optoelectronics, photovoltaic[19], bio imaging[20],
and photodynamic therapy[18]. The parent compound 1,3,5,7-tetraphenylaza–BODIPY (TPAB)
shows absorption and emission around 650, and 672 nm, respectively, and various methods have
been developed to alter their optical properties i.e., absorption and emission range towards the NIR
range with better quantum yield values. However, as the synthesis of aza-BODIPYs includes a
complicated synthetic procedure with multiple reactions getting lower yields, their applications are
limited in several fields. We were fascinated in developing a collection of NIR Aza–BODIPYs con-
taining Bis(4 0 -tert-butylbiphenyl-4-yl)aniline on Aza-BODIPY core with a simple straightforward
synthetic method. The efficiency of solar cell can be calculated by using following equation:

JSC × VOC × F F
η=
Pin
The Over all efficiency of solar cell is depends on the η.
Where,

15
 Figure 4.1: Whole Energy Spectrum

Figure 4.2: Aza-Borondipyrromethenes

• η = Efficiency of solar cell

• JSC = The actual current density of the system

• VOC = The actual potential difference of the system

• F F = fill factor(ratio of actual value and maximum value)

• Pin = The total light power density or total power

Improving overall solar conversion efficiency needs:

• Jsc a greater absorption of the incident light

• Panchromatic dyes ( By increasing the absorbance efficiency of dye)

• High molar absorptivity of dyes

4.2 What is BODIPY Dyes ?

In many previous studies [4], the structure of BODIPY has been compared to a rigid tannin structure
as shown in figure 4.3 and 4.4. The flexibility is restricted and therefore the bodipy is having

16
high fluorescence yields from the dipyrromethene boron framework. Conjugation of the p-electrons
runs along the organic backbone and can be extended by condensation of suitable groups onto the
periphery or by the attachment of conjugated units to one or both pyrrole fragments. The numbering

Figure 4.3: Basic types of cyanine structure [4]

is as follows:

Figure 4.4: Numbering scheme used for the Bodipy framework derived from indacene [4]

All properties especially those relating to fluorescence and other photophysical properties are
dependent on the resonance that is how electrons are delocalized and in other words by the donor and
acceptor characteristics of the pyrrole substituents. Therefore current research aimed at modifying
the characteristics of BODIPY dyes by calculatively introducing functionalities at the electron dense
positions in the BODIPY. Most substitutions are made on the 8th position also referred to as the meso
position[21]. A key point is that pyrrole substituent restrict rotation of aromatic groups attached at
the 8-position and the resultant orthogonal geometry serves to minimize electronic coupling between
the dye and the meso substituent.
BODIPY dyes that do not have any substituent on the 2nd and 6th position are able to undergo
electrophilic reactions in the presence of chlorosulphonic acid[22]. In order to make these dyes useful
for biomedical applications theri water solubility is important so that they are compatible with the
biological system itself. Hence, hydrophilic groups are substituted on these positions to ensure water
solubility.
Obtaining F-Bodipy dyes exhibiting fluorescence in the far-red or near-IR regions of the spectrum
requires the presence of an extended delocalization pathway. Several strategies are available by which
to build this type of Bodipy dye. The most direct method is to synthesize pyrrole derivatives bearing

17
phenyl, vinyl, or thiophene groups at the 3-position [23] .
Also, there are some papers on studies regarding substitutions made on the boron center rather than
on the carbons. Aryl groups have been substituted on the boron instead of the fluorine. Ulrich et.
al[4] have made use of an organometallic route to carry out this reaction and it can be done by using
phenyl magnesium chloride as the reagent. These greatly increase the versatility of BODIPY and
also allows the isolation of molecular triads, tetrads.
One other interesting modification in the conventional BODIPY framework is the modification of
one carbon bridge that connects the two pyrrole rings and will be elaborated in the next section.

4.3 Aza-Borondipyrromethenes and its synthesis

3a,4a,8-triaza indacene dyes are referred to as aza-bodipy dyes, They have increased fluorescence
in the far-red and near-IR regions of the spectrum. The meso carbon atom is replaced in the
dipyrromethene with an aza-nitrogen atom (N). The nitrogen lone pair at the 8-position appears to
contribute to the orbital levels of the actual cyanine framework, reducing the HOMO–LUMO energy
gap relative to Bodipy dyes bearing similar substituent. A typical structure of Dye we have synthesis
in our lab is shown in figure 4.5. We have made some change to extend its conjugation, in order to

Figure 4.5: Aza-Borondipyrromethenes

get the molar absorptivity of our need. The synthesis of unsymmetrical Aza-Borondipyrromethenes
(AzaBODIPYs) will be discuss upcoming portion.

4.4 Results and discussion

4.4.1 Synthesis Details
The synthetic pathway of preparation of TNAZDPM( tolyl napthalene Azadipyrromethene) in figure
4.6. The step by step preparation tolyl napthalene Azadipyrromethene is discussed in upcoming

18
 Figure 4.6: Synthetic pathway of preparation of TNAZDPM

subsection with there respective spectra as an proof of their presence.

4.4.2 Synthesis of TNCHAL (tolyl napthalene chalcone)

4-(di-p-tolylamino)benzaldehyde (0.00165 mol) was dissolved in 20 mL ethanol and 1-(naphthalen-1-
yl)ethan-1-one (0.00165 mol) were added, followed by the addition of 10 % ethanolic KOH solution
and stirred for more than 24 h with constant stirring in a magnetic stirrer under nitrogen condition.
The reaction was monitored by TLC. After completion of the reaction, solution was cooled and
neutralized with con. HCl (1M). The compounds were purified by column chromatography using
silica gel using hexanes and ethylacetate (5:95 v/v). 1H NMR (500 MHz, CDCl3 ): δ 8.28 (d, 1H),
7.98 (d, 1H), 7.91 (d, 1H), 7.70 (dd, 1H), 7.54 (m, 4H), 7.37 (dd, 2H), 7.13 (m, 5H), 7.04 (m, 4H),
6.94 (dd, 2H) Yield: 85 %.

Figure 4.7: Preparation pathway of TNCHAL

19
 Figure 4.8: NMR of TNCHAL

NMR of TNCHAL

The spectra is shown in figure 4.8

4.4.3 Synthesis of TNNO2 (tolyl napthalene nitro)

To the solution of compound TNCHAL ( 0.00138 mmol), nitro methane (20 mL),and
1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) (0.2622g, 6.9 mmol) refluxed for 24 h. The reaction was
monitored by TLC. The solution was cooled, acidified with hydrochloric acid (1M) and extracted us-
ing DCM. Crude product was purified by column chromatography using hexanes:ethylacetate (10:90
v/v) as the eluent. 1H NMR (500 MHz, CDCl3 ),δ8.38 (d, 1H), 7.99 (d, 1H), 7.86 (dd, 1H), 7.78 (dd,
1H), 7.56(m, 2H), 7.49 (m, 1H), 7.07 (m, 6H), 6.95 (m, 6H), 4.80 (q, 1H), 4.70 (q, 1H), 4.20 (qui,
1H),3.51 (dd, 2H), 2.31 (s, 6H) Yield: 95%.

20
 Figure 4.9: Synthatic Pathway of TNNO2

NMR spectra of TNNO2

The spectra is shown in figure 4.10

4.4.4 Synthesis of TNAZDPM(tolyl napthalene Azaboron dipyrromethene)

The mixture of appropriate TNNO2 derivative and ammonium acetate 50(eq) was refluxed in n-
butanol(30ml) for 24h. Under nitrogen gas the reaction was monitered by TLC. The reaction mixture
in the round-bottomed flask was allowed to cool to room temperature. Then CH2 Cl2 (200 mL) and
water (50mL) was added. The organic layer was separated, washed with water (3 × 50 mL) and dried
over sodium sulphate. The solvent was evaporated to give the product as a dark blue solid.Crude
product was purified by column chromatography on silica gel using chloroform and hexane (20: 80
v/v) as the eluent. 1H NMR (500 MHz, CDCl3 ): δ8.80 (d, 2H), 7.98 (d, 4H), 7.92 (m, 7H), 7.53 (s,
1H), 7.51 (m, 7H), 7.13 (dd, 2H), 7.09 (s, 2H), 7.06 (d, 4H),7.04 (s,10H),6.99 (d,1H), 6.97 (d,1H),
2.30 (s,12H), ESI-MS: [M+H]+ calculated: 940.4379; found: 940.4385.Yield: 60 %.

NMR and MS-Spectra of TNAZADPM

The spectra is shown in figure 4.12 and 4.13

4.4.5 Synthesis of TNBAZDPM

The solution of compound TAZDPM (0.1969mm) in dry DCM was treated with DIPEA(1.969 mm,
0.342 ml) and stirred for 30 min under nitrogen condition at room temperature.Then the solution
of of BF3 · Et2 O (1.43 mmol, 203 mg) was added drop-wise and the mixture was stirred 24h at
room temperature.Then the reaction mixture was slowly quenched with water and extracted with
chloroform and dried over sodium sulphate. The solvent was evaporated to give the product as a dark
blue solid.Crude product was purified by column chromatography on silica gel using 30 % chloroform
and hexane solvents. 1H NMR (500 MHz, CDCl3 ):δ 7.92 (dd, 2H), 7.81 (m, 7H), 7.46 (m, 7H),
7.00 (s, 14H), 6.97 (m, 3H), 6.94 (d, 2H), 6.92 (d, 1H), 6.70 (s, 2H),), ESI-MS: [M+ H]+ calculated:
988.4362; found: 988.4362.Yield: 95%. The synthetic pathway is shown in figure 4.14

21
 Figure 4.10: NMR spectra of TNNO2

Spectra of the Final dye

Absorbance spectra shows that the dye do show the absorbance in the visible range light which is
400 to 700 nm approximately. the absorbance spectra of TNBAZDPM is shown in figure 4.17 and
its NMR and Mass spectra is shown in figure 4.16 and 4.15 respectively.

22
Figure 4.11: Preparation of TNAZDPM from TNNO2

23
Figure 4.12: Mass Spectra

24
 Figure 4.13: Mass spectra of TNAZADPM

Figure 4.14: Synthetic pathway of preparation of TNBAZDPM

25
Figure 4.15: Mass spectra of TNBAZDPM

26
Figure 4.16: NMR of TNBAZDPM

27
Figure 4.17: Absorbance Spectra of TNBAZDPM

28
Conclusion

A research problem comprised of the synthesis of panchromatic aza-BODIPY dyes for their appli-
cations as light harvesting devices has been chosen and the related literature has been thoroughly
reviewed. In the regard to the synthesis of the panchromatic aza-BODIPYs,fictionalized with triph-
enylamine and naphthalene chromophores and its precursors, chalcone and nitro have been synthe-
sized and fully characterized using 1H NMR and ESI-MS studies.

29
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