Synthesis, Characterization,

Photophysical and Thermal

Properties of AIE Active
Polymers

ABHISHEK RAJ
2013B2A4224P
 OVERVIEW
Background

Experimental

Results and discussion

Conclusion

Future scope of work

Bibliography
 BACKGROUND
Polymer: Large molecule built up by the repetition of small simple chemical
units.

Poly(many) + mers (part)

 EXAMPLES OF POLYMERS
Very wide range of materials , applications

Very wide range of physical forms - Solid Liquid Emulsions

 AGGREGATION INDUCED
EMISSION (AIE)
The phenomenon in which organic luminophores show higher
photoluminescence efficiency in the aggregated state than in solution is
called aggregation-induced emission (AIE).

The main principle of the AIE effect can be attributed to restricted

intramolecular rotation (RIR) of its phenyl peripheries against the central
double bond in the aggregate state
 Example of AIE

TPE - Tetraphenylethene HPS Hexaphenylsilole

 AIE vs ACQ
AIE Aggregation Induced Emission ACQ Aggregation Caused Quenching

Examples TPE ,Hexaphenylsilole Examples Pyrene , Fluorescein

(HPS),
ADVANTAGES OF AIE POLYMERS
Compared with small AIE molecules, AIE polymers show additional
advantages.

Film Forming Thermal

ability Stability

Mechanical Environmental
Strength Stability
APPLICATIONS
 Why TPE?
Triphenylethylene derivatives have excellent thermal properties

It also has excellent blue light emission capabilities in aggregated state.

The twisted configuration of Triphenylethylene has been considered to be a

key structural factor for the AIE property of these derivatives.

Easy Synthesis and functionalization of compound .

 LITERATURE SURVEY
1. Synthetic routes to BDTPE and BBTPE.
2. Synthetic route of DTPC
 PROCEDURE

4methyl Dibromo
Di Methyl TPE TPE aldehyde TPE polymer
benzophenone Methyl TPE

Ylide TPE
 Synthesis of 4-methylbenzophenone

Temp: 80oC reflux

Time: 3.5hr
Yield: 80%

Reaction procedure followed by Work up process.

Product was obtained by recrystallization using EtOH
Synthesis of Methyl Tetraphenylethene:
McMurry Reaction

Temp: 80oC reflux

Time: 12 hr
Yield: 50%

Reaction procedure followed by Work up process.

Product purified by Column Chromatography using 100% Hexane as eluent.
 Bromination of Dimethyl TPE

Reaction procedure followed by Work up process.

Product purified by Column Chromatography using 100% Hexane as eluent.
 Synthesis of TPE dialdehyde: Kornblum
oxidation

Reaction procedure followed by Work up process.

Product purified by Column Chromatography using 100% Hexane as eluent.
Synthesis of Polymer

Phosphonium Ylide formation

Polymer formation
using Wittig
reaction
 Results and Discussion
Aldehyde monomer was formed from 4-methyl Benzophenone after 4 steps.

Using the aldehyde monomer and Ylide compound, polymer was

synthesized.

Under UV light the dry compound shows Emission but in solution the
emission is not present.

Hence AIE activity of compound is confirmed.

Problems with Preparing the
compound
Low Yield
The yield of the final monomer product was very low.
20 g of starting material was used and only 20mg of product was obtained.

Purity of Aldehyde compound

The aldehyde compound had many side products.
Separation required the use of 100% hexane as eluent as the product and
by-product spots were very close.
Due to this the separation process took more than 8 hrs.

Stability of Product
The impure aldehyde compound was not stable under normal conditions
while doing column chromatography.
It required the use of basified silica using trimethylamine for the
compound to remain stable while doing column chromatography.
 1H NMR

singlet
doublet

triplet
 13C NMR

Ketone
 1H NMR

Doublet

Multiplet Singlet
13C NMR
 1H-NMR Spectrum of TPE-(CH2Br)2

Aromatic
Hydrogen
of
Substituted
Ring

Aromatic
Hydrogen (CH2Br )2
 1H NMR

Solvent
Aromatic
Peak
H of ring
with
CHO
Aldehyde
H Aromatic
H Aromatic
H of ring
with
CHO
 Future Scope of Work
Polymer formation with the monomers prepared.

IR spectroscopy for determining the molecular structure.

Gel Permeation Chromatography to find molecular weight of the polymer.

Differential scanning calorimetry and thermogravimetric analysis for

thermal analysis of the polymer.
 Bibliography
Tetrahedron Letters,Volume 57, Issue 39, 28 September 2016, Pages
4428-4434

(b)Y. Liu, Y.H. Tang, N.N. Barashkov, I.S. Irgibaeva, J.W.Y. Lam, R.R. Hu,
D. Birimzhanova, Y.Yu, B.Z. Tang ,J. Am. Chem. Soc., 132 (2010), p. 13951

Chem. Sci., 2015,6, 5347-5365

ACS Appl. Mater. Interfaces, 2017, 9 (34), pp 2833128338

X.-F. Duan, J. Zeng, J.-W. L, Z.-B. Zhang, J. Org. Chem., 2006, 71, 9873-
9876.
THANK YOU
 ACQ
Conventional fluorophores, such as fluorescein, are usually fluorescent when
they are in dilute solution.

Their fluorescence is decreased or quenched when the concentration is

increased.

Most of these conventional fluorophores adopt flat disc-like shapes, which

would easily undergo strong stacking interactions when they are in close
proximity in the concentrated solution or aggregate state.

In such situation, the excited states often decay via nonradiative decay
pathways, which is known as the aggregation-caused quenching (ACQ) of
light emission.
Mechanism

Friedel craft acylation

Mechanism
Mechanism
 SEPARATION
2 spots were obtained which were separated by column chromatography.

100-200 mesh silica gel was used.

Solvent used was 100% hexane.

Final TLC of the product after separation.

1 spot 2 spots
 SEPARATION
2 spots were obtained which were separated by column chromatography.

100-200 mesh silica gel was used.

Solvent used was 100% hexane.

Final TLC of the product after separation.