Solvatochromism and Fluorescent Enhancement Study of N,N,N′,N′-tetramethyl-p-phenylenediamine

by Substitution of Cyano Group(s) on the Aromatic Ring

Zahid, M.a), Graz/A, Grampp, G.a), Graz/A, Rosspeintner, A.b), Geneva/CH, Landgraf, S.a), Graz/A
a) Institute of Physical and Theoretical Chemistry,Graz University of Technology, Austria
E-mail: zahid595@gmail.com
b) Physical Chemistry Department Sciences II, University of Geneva, Switzerland

Introduction
Substitution of cyano (-CN) groups on p-phenylenediamine (PPD) and N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPPD) dramatically change both, electrochemical and
photophysical properties (fluorescence quantum yield and lifetime) e.g. in tetracyano-p-phenylenediamine (TCPPD) [1] and 2,6-dicyano-N,N,N’,N’-tetramethyl-p-phenylenediamine
[2]. This makes it interesting to know how the behavior of PPD/TMPPD is changing with different substitution of cyano groups on the aromatic ring. Photophysical of TMPPD and
monocyano-substituted TMPPD, 2-cyano-N,N,N′,N′-tetramethyl-p-phenylenediamine (TMMCPPD), have been studied in different solvents.

Photophysical study of MCPPD and TMMCPPD

Photophysical Study Solvatochromism and LSER analysis
The photophysical properties have been studied in various solvents covering a wide The effect of different solvents on absorption and fluorescence spectra of PPDs are
range of the both, Kamlet-Taft (, β and ∗)[3] and Catalan (SA, SB, Sdp and Sp) [4] analyzed by means of two empirical solvent parameter scales, namely those
solvent parameter sets. The effect of solvents on absorption and fluorescence spectra developed by (a) Kamlet-Taft and Catlan. This approach accounts for both specific and
has been studied by applying Linear solvation energy relationship (LSER). non-specific solvent-solute interactions in a type of linear energy relationship
ABC  ABCo  xX  yY  zZ
Absorption and Fluorescence Spectra where X, Y and Z are the parameters describing the solvent and x, y and z are the
Cyclohexane
respective contributions of the solute.
Cyclohexane
Acetonitrile Acetonitrile
0.9 DMSO 0.9 0.9 DMSO 0.9 Experimentally determined fluorescence maxima Experimentally determined fluorescence maxima
Normalized Fluorescence (Iflu()/ )
Normalized Absorption (Iabs()/)

Normalized Fluorescence (Iflu()/ )

3

3
Normalized Absorption (Iabs()/)

of TMPPD versus corresponding theoretically of TMPPD versus corresponding theoretically

calculated values using Kamlet-Taft parameters calculated values using Catalan parameters
26
 flu  25.64  0.55  0.06  1.30 *  flu  27.30  1.03SA  0.06 SB  0.86Sdp  2.58Sp
2 1
0.6 0.6 0.6 0.6
2 1 25.5 R  0.970
25.5
R  0.983 7
8
7

8
11 9
10
9 25 56
0.3 0.3 0.3 0.3 25 11 6 10
5
o 4
 flu (exp) / kK 4  flu (exp) / kK
16 242122
16 2119 24.5 1915
24.5 24 22 15 1823
23
0.0 0.0 0.0 0.0 25 17 18 1725

24 24
40 35 30 25 20 15 40 35 30 25 20 15
Wavenumber (kK) 26 26
Wavenumber (kK)
Absorption (dashed line) and fluorescence (solid line) of TMPPD in DMSO ( ), 23.5 23.5
Absorption (dashed line) and fluorescence (solid line) of TMMCPD in DMSO ( ), 23.5 24 24.5 25 25.5 26 23,5 24 24.5 25 25,5
acetonitrile ( ) and cyclohexane ( ). ( ) is the complete normalized absorption acetonitrile ( ) and cyclohexane ( ). ( ) is the complete normalized absorption  flu (theo) / kK  flu (theo) / kK
spectrum of TMPPD in acetonitrile spectrum of TMMCPPD in acetonitrile.

o
o
Photophysical Properties Experimentally determined fluorescence maxima
of TMMCPPD versus corresponding theoretically
Experimentally determined fluorescence maxima
of TMMCPPD versus corresponding theoretically
The photophysical properties like absorption and fluorescence maxima, Stokes shift calculated values using Kamlet-Taft parameters calculated values using Catalan parameters
(), 0-0 transition energy (E00), fluorescence quantum yield (), fluorescence lifetime 22.5
 flu  22.42  0.45  0.15  1.44 * 1 22.5  flu  23.79  0.81SA  0.03SB  1.13Sdp  2.13Sp 1

2
R  0.981
(), radiative (kr) and non-radiative (knr) rate constants for MCPPD and TMMCPPD in R  0.986 2
7
some representative solvents are shown below. List of solvents used for investigation of 22 8
7
22 8

photophysical properties along with their abbreviations are shown. 1195 3 5 3

 flu (exp) / kK  flu (exp) / kK 11 9
6 6
4 21.5 4
1 n-Hexan NHX 7 Butylether NBE 13 Benzonitrile BCN 21 1-Butanol 1BOL 21,5
12 12
16 2219
o 16 2219
2 Cyclohexan CHX 8 Diethyl ether DEE 14 Dimethylsulfoxide DMSO 22 2-Propanol 2PROL 23 21 15
24 18
21
18 24 15
21 21 23
25 25
3 p-Xylene XYL 9 Propylacetate PRA 15 Acetonitrile MeCN 23 1-Propanol 1PROL 17 17

4 Benzene BZN 10 Ethylacetate ETA 16 Dimethylformamide DMF 24 Ethanol EtOH 20,5 26 20.5 26

5 Toluene TOL 11 Tetrahydrofurna THF 18 Prpylene carbonate PrC 25 Methanol MeOH 20.5 21 21.5 22 22.5 20.5 21 21.5 22 22.5

6 Tthylbenzene ETB 12 Acetone ACT 19 1-Pentanol 1ptol 26 Water H2O  flu (theo) / kK  flu (theo) / kK

TMPPD  TMMCPPD
abs (kK )  flu (kK )  E00  kr knr abs (kK )  flu (kK )  E00  kr knr

Solvents (cm-1) (kJ/mol)  (ns) (107s-1) (107s-1) (cm-1) (kJ/mol) (ns) (107s-1) (107s-1)
n-Hexan 30.59 25.74 4844 337 0.17 4.3 4.01 19.36 27.23 22.59 4641 298 0.58 14.6 3.98 2.87
Benzene 30.07 24.77 5293 328 0.54 7.8 6.90 6.00 26.57 21.59 4989 288 0.77 16.6 4.66 1.36
Ethyl ether 30.51 25.41 5094 335 0.15 3.7 4.09 22.88 27.05 22.06 4987 294 0.66 17.3 3.84 1.94
DMSO 30.35 24.31 6034 327 0.28 8.8 3.17 8.25 26.33 20.88 5449 282 0.81 19.9 4.05 0.98
Ethanol 31.35 24.50 6841 334 0.25 7.2 3.46 10.51 26.83 21.08 5751 287 0.10 2.6 3.86 34.6
Methanol 31.58 24.31 7277 334 0.10 3.7 2.82 24.34 26.92 20.93 5992 286 0.004 0.85 3.31 114.34

Comparison of photophysical properties of cyano substituted TMPPDs

25 H2O H2O -1.5
MeOH MeOH -2.5

EtOH EtOH TMPPD

20
PrC 0.6 PrC TMMCPPD
-2.0
DMSO DMSO TMDCPPD
Quantum Yield

15 -1.0
Lifetime (ns)

MeCN DMF
THF MeCN TMPPD
Value

-1.5
THF TMMCPPD
Value

10 DEE 0.3 DEE TMDCPPD

BZN
CHX BZN -0.5 -1.0
5
NHX CHX
NHX
0 -0.5
0.0
0.0
TMPPD TMMCPD TMDCPD TMPPD TMMCPD TMDCPD 0.0
 SA SB SDP Sp
Solute Solute Kamlet-Taft paramters
Comparison of fluorescence quantum yields of TMPPDs in different solvents Catalan's Parameters
Comparison of fluorescence lifetimes of TMPPDs in different solvents Comparison of Kamlet-Taft paramters for three TMPPDs
Comparison of Catalan's paramters for three TMPPDs

Conclusions: References:
Both lifetime and quantum yield has been increased dramatically upon inclusion of the [1] G. Angulo, G. Grampp, J. Grilj, P. Jacques, S. Landgraf, A. Rosspeintner, J. Photochem.
cyano groups on the aromatic ring. Both absorption and fluorescence spectra are shifted Photobiol. A: Chem. 2008, 199, 204.
bathochromically with increase the number of cyano groups. Solvatochromism of all
three cyano substituted TMPPDs are mainly governed by solvent [2] A. Rosspeintner, G. Angulo, M. Weiglhofer, S. Landgraf, G. Grampp, J. Photochem.
polarity/polarizability term with a little contribution of solvent hydrogen bond Photobiol. A: Chem. 2006, 183, 225.
donating ability. [3] M. J. Kamlet, J. L. M. Abboud, M. H. Abraham, R. W. Taft, J. Org. Chem. 1983, 48,
2877.
Acknowledgement: [4] Javier Catalan, Journal of Physical Chemistry B 2009, 113, 5951-5960.
Higher Education Commission (HEC) Pakistan for funding my PhD studies is
gratefully acknowledged.