Luminescent self-assembles: Challenges and recent

advances

Aniket Chowdhury
Prof. Partha Sarathi Mukherjee’s Group
Inorganic and Physical Chemistry Department
Indian Institute of Science
Bangalore

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 Background information

8+

1. AgNO3, 5 h

2. acetone, 60 oC NACs

2 eq 4 eq 12h

8 NO3
P. S. Mukherjee et al. Inorg. Chem.
2012, 51, 13072-13074

MeOH,CHCl3, 60 oC
24h
3 eq 2 eq
P. S. Mukherjee et al. Dalton trans.
2013, 42, 16784-16795

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 Solid state emission
When solidified the fluorescence of the luminophores quenches
due to formation of aggregates by p-p interactions

Steric hindrance Aggregation induced emission

AIE

Restriction of
Intramolecular
HPS Solution rotation Solid

T. Akutagawa et al. Cryst. Eng. B. Z. Tang et. al. Chem. Rev. 2015, 44, 4228. 3
Comm. 2014, 16, 3180.
 Molecular systems for AIE
Tetraphenylethylene and Hexaphenylsilole derivatives were the first among AIE-gens:

J. Xu et al. J. Mater.Chem. 2011, 21,

1788-1796 B. Tang et al. Chem. Rev. 2015, 115,
11718-11940
Vinylanthracene is recently exploited for high solid-stat emission and AIE behaviour:

A. Siva et al. New. J. Chem. 2016, 40,

5099-5106
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 Restricted Motion

DCM, r.t

F. Huang et al. Nat. Chem. 2015, 7, 340-348.

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H and 31P NMR spectra of the building block and final assembly:

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 Increased emission by Restricted Motion
Tetraphenylethylene exhibit AIE behaviour in high water THF mixture:

Drawbacks:
1.Total restricted motion inhibit the enhancement factor.

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Emission enhancement by partially restricted motion

DCM, r.t

3 eq

3 eq

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 Synthesis of AIE-active donor

TPEE, NEt3, CuI

4-BrPy, NEt3, CuI
Pd(PPh3)2Cl2, PPh3
Pd(PPh3)2Cl2, PPh3

K2CO3, DCM,
MeOH
TPEE, NEt3, CuI
Pd(PPh3)2Cl2, PPh3

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Emission enhancement by partially restricted motion
 The partially free TPE centre exhibits Stronger
AIE effect than previous molecule
 The final assembly is cationic (6+). Heparin-
induced aggregate formation lead to enhanced
emission in solution.

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 Previous work

A. Chowdhury, P. Howlader, P. S. Mukherjee Chem. Eur. J. 2016, 22, 7468-

7478.c

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Synthesis of the acceptors

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Synthesis and characterization

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 Aggregation induced emission

o With increasing hexane

Compound 5 Compound 7
fraction in DCM
solutions of 5 and 7,
increase in emission
intensity was observed.

o The emission increased

up to 80% hexane
fraction in DCM before
Change in fluorescence intensity of 5 (left) and 7 (right) attaining saturation.
with various hexane fractions in DCM
o The extent of
enhancement was higher
for 5 than 7.

o The aggregates
formation was
investigated by DLS
analysis, SEM and TEM
experiments.
Images of vials containing solutions of 5 with different hexane fraction in DCM under 13
UV light
 Particle size analysis

Particle size analysis of 5 with different hexane fraction in DCM, 60% (left) and 80% (right)
 DLS revealed formation of
aggregates in different
solvent compositions.
 The size of the aggregates
increased with increasing
hexane fraction.
 The TEM and SEM images
revealed that the aggregates
are spherical in nature.

SEM analysis of 5 with different hexane fraction in DCM, 60% (left) and 80% (right) 14
 What next?

AIE centre Photochromic donor

AIE active and

photochromic self-
assembly
3 eq 3 eq

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 AIE active acceptor

AgNO3, CHCl3, Toluene, NEt3, CuI

MeOH Pt(PEt3)2I2

K2CO3, CHCl3,
MeOH

TMSA, NEt3, CuI

THF, KtBuO, BP Pd(PPh3)2Cl2, PPh3

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 AIE active acceptor

EtSp, NEt3, CuI BrPy, NEt3, CuI

Pd(PPh3)2Cl2, PPh3 Pd(PPh3)2Cl2, PPh3

K2CO3, CHCl3,
MeOH

TMSA, NEt3, CuI

HOAc, Ki, KIO3 Pd(PPh3)2Cl2, PPh3

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Intermediates

EtOAc
DCM

EtOAc
EtOAc

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Thank You

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