Recent advances in mechanoluminescent materials

 Mechanoluminescence, what is that?

 Is it really that important?

 How does it work?

 Recent literatures

 What can we do?

 Mechanoluminescence

 Mechanoluminescence, what is that?

Mechanoluminescence/triboluminescence is the radiative emission generated by

crystalline materials upon application of different types of mechanical force including
grinding, shearing, rubbing etc.

The word ‘triboluminescence’ which came from the greek word ‘triben’ was coined by
Prof. G. Widemann in 1985.

Mechanoluminescence of sugar was first reported by Francis Beacon in 1605.

 Applications

 Is it really that important?

Mechanoluminescent materials have found their way into real-time sensor for monitoring
mechanical stress, checking structural damages, as secondary X-ray source, in new display
devices.

 Chem Sci., 2016, 7, 5307

No of papers with time
 Mater. Horiz., 2016, 3, 220
 JOC., 2016, 81, 433
300
 Angewchem., 2016, 128, 1
250
 Angewchem., 2015, 127 888
 Chem. Sci., 2015, 6, 3236
130
 Chem. Mater., 2012, 24, 671

45
15
1600-1900 1901-1960 1961-1990 1991-2000 2001-2013
 Types of ML materials

 According to literature estimates, 36% of inorganics, 19% of organics, 37% of aromatic

compounds, 70% of alkaloids and perhaps 50% of all crystalline materials are
triboluminescent.

 Sucrose, tartarc acid, cadmium sulphate, uranyl nitrate, coumarin, isopropyl carbazole,
anthracene carboxylic acids, acenapthene etc. are well known ML materials.

 Materials which crystallise in non-centrosymmetric space groups are prone to exhibit ML

behaviour.

 Depending on working principle the ML materials can be divided into discharge and non-
discharge based ML materials.

Chem Mater., 2001, 13, 854-870

 Discharge-based ML materials

 When molecules are crystallised in non-centrosymmetric space groups they

generate stable dipole moment in the medium.

 Exertion of external pressure create cracks in the crystal with oppositely charged
surface.
--
++ -
++ -
 Charge recombination creates electronic discharge which excites the nitrogen
present in the medium. The excited nitrogen releases the energy in UV emission
form with sharp peaks at 337, 358 and 380 nm. Those UV emission is absorbed by
the surrounding fluorophores and they exhibit emission which is comparable to
their PL spectra.
 Non-discharge-based ML materials

 Exertion of external pressure combines oppositely charge defects as dislocation of crystal

planes sweep them into collision. This ML behaviour is environment independent and
occurs throughout the bulk material, not in the cracks or fissures of crystal planes

Grinding
hv

 The energy released after defect recombination, is absorbed by nearby fluorophores which
then exhibit ML behaviour. The release and reabsorption of energy is instantaneous
process. The ML spectra often resembles with the electroluminescence spectra rather than
PL spectra.

 Doped alkali halides, zinc sulphides crystals contain crystal defects, grain boundaries and
chemical impurities which contains trapped electrons and holes. They can be recombined
by motion of dislocations under strain, just as they are released by applied voltage.
 Exceptions

 Several ML molecules are known which crystalize under centrosymmetric space groups.
Centrosymmetric ML materials

Impurities which are itself ML active Generation of partial non-

centrosymmetric regions due to
crystal deformation or disorders
 The ML behaviour of saccarin is traced back to the impurities p-toluene sulphonamide
and p-sulfoamoylbenzoic acid. After double recrystallization from water-acetone
mixture it loses ML property..

 Bond rupture can release electrons, charge separation by partial surface fracture can also
occur. For organic compounds deformation may change the local structure from that
observed by X-ray diffraction, generating sites of local dissymmetry (supported by SHG
as observed by Nd:YAG lasers) which can support charge separation.
 Criteria for ML materials

 An asymmetric molecules is always favoured as it has the better possibility to pack in

non-centrosymmetric fashion.

 Molecules with permanent dipole (Donor-p-Acceptor systems) will retain a net

macroscopic dipole after crystallization.

 Highly twisted backbone have the advantage of restricting p-p interactions during
packing.

 Attachment of chiral centre increases the possibility of non-centrosymmetric packing.

 Different functional groups like –CHO, -CN, increases weak interactions in the motif
which increases the energy migration among neighbouring molecules.

 Inclusion of AIE active centres increases the ML quantum yield.

 ML materials with flat p surfaces
O O

N CF3 N CF3

O O

D--p--A D--p--A
N-phenylimides acts as the donor molecules to the trifluorocarbon acceptor.

The asymmetric structure helps to pack the molecules in non-centrosymmetric space

group during crystallization.

Chem. Mater. 2012, 24, 671-676

 Crystal structure
The molecules crystallizes in non centrosymmetric
space group Cc, with the CF3 groups oriented in the
same direction and in b herringbone pattern,
resulting a large net dipole moment.

The phenyl ring orients itself with a dihedral angle

of 57.6o with the imide ring resulting a twisted
packing with less p-p interaction among aromatic
planes.

Upon grinding with spatula, green flashes were

observed from the crystals which resembles their
PL spectra indicating that the ML is following the
discharge mechanism.

The PXRD pattern before and after grinding

indicated the retaintvity of crystalline nature
 Structure modification for ML tuning
LUMO
O
LUMO
S S
N CF3
DE DE
O HOMO
D--p--A HOMO
This work

Previous sample
The extended conjugation decreases the HOMO-LUMO
energy gap. The smaller energy gap red shifts the
emission to 598 nm from 490 nm.

During grinding with spatula red flashes were observed

from the glass beaker.

JOC. 2016, 81, 433-441

 Drawbacks and new approach
Problem:
The flat aromatic donor part has the tendency to increase p-p interaction in solid- state
which reduces the quantum yield.

In the solution the molecules forms aggregates with the polyaromatic region oriented in
excimeric fashion. Thus their solution emission efficiency is drastically low.

Solution:
Attachment of AIE active centres like tetraphenylethylene increases the solid-state
quantum yield.

The propeller shape of the molecule also demonstrate variation of emission intensity
with temperature. Reducing the temperature freezes the rotation of the aromatic rings
increasing the radiative emission.
 Enhanced ML with AIE behaviour
Temperature sensor and AIE

Twisted D--p--A
The crystal structure indicates highly twisted nature of the molecules packed in non-
centrosymmetric P21 space group.

The aldehyde groups are hydrogen bonded with neighbouring molecules which help in
energy migration.
 Enhanced ML with AIE behaviour
Gradual water addition to the THF solution slowly
increases the emission intensity.

At high water fraction >90% the intensity increases 54-

fold.

The appearance of long wavelength tails in absorption

spectra indicates Me scattering due to formation of
spherical aggregates in the medium.
Gentle crushing of the crystals generates blue flashes in the medium.

The resembles of the ML and Pl spectra indicates discharge

mechanism.
 What can be done
The synthesis of new ML dyes can be accomplished using the following principles

Donor Acceptor
-NR2, -thiophene, -OR, -CHO, -CN, -BR2,-NO2,-CF3 etc
The molecules must contain a donor-acceptor
pair to induce permanent dipole in the system.

A highly twisted aromatic core increases ML

efficiency by decreasing intermolecular
interactions.

Different aromatic core including TPA,

TETPE, TRB, DVAn can be used both as donor
and aromatic core
Thank You