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Synthesis, spectroscopic, electrochemical redox,

solvatochromism and anion binding properties of
b-tetra- and -octaphenylethynyl substituted meso-
Cite this: RSC Adv., 2015, 5, 82237

tetraphenylporphyrins†
Ravi Kumar, Pinky Yadav, Pinki Rathi and Muniappan Sankar*

b-Tetra/octa-phenylethynyl substituted porphyrins and their metal (Co(II), Ni(II), Cu(II) and Zn(II)) complexes
have been synthesized and characterized. H2TPP(PE)8 exhibited a remarkable red shift in the Soret (Dlmax ¼
92 nm) band and longest wavelength band, Qx(0,0) (Dlmax ¼ 117 nm), as compared to H2TPP. Interestingly,
MTPP(PE)8 exhibited a 450–500 mV anodic shift in the first ring reduction potentials as compared to MTPP
which is ascribed to the electron accepting nature of phenylethynyl groups and extended p-conjugation
whereas the first ring oxidation potentials remain unaltered. Hence, we observed a significant reduction
in the HOMO–LUMO gap. The fluorescence quantum yields and lifetime values of the free base and
Zn(II) porphyrins are found to be 10–20 and 2–6 times, respectively lower than MTPPs. These porphyrins
display a strong solvatochromism that is reflected by a large red-shift in their absorption and emission
maxima upon increasing the solvent polarity. These porphyrins exhibited lower radiative rate constants
(kr) and enhanced nonradiative rate constants (knr) as compared to MTPPs. The decrement in
fluorescence lifetime values, quantum yields, radiative rate constants (kr) and profound solvatochromism
with enhanced nonradiative rate constants (knr) have been interpreted in terms of intramolecular charge
transfer (ICT) from the porphyrin core to phenylethynyl moieties and extended p-conjugation. Further,
Received 30th July 2015
Accepted 23rd September 2015
ZnTPP(PE)8 was utilized for the colorimetric “naked-eye” sensing of CN, F, Cl, Br, H2PO4 and
CH3COO ions through axial coordination of anions to Zn(II) metal centre. The electron deficient nature
DOI: 10.1039/c5ra15211a
of the Zn(II) centre of ZnTPP(PE)8 was further proved by axial ligation studies with anions in toluene.
[Link]/advances ZnTPP(PE)8 exhibited extremely high binding constants (1012 to 107 M2) with anions.

phyrins exerts much larger steric and electronic effects on the

Introduction porphyrin p-system.8
Substituted porphyrins have unique electronic and optical Notably, meso-phenylethynyl appended ‘push–pull porphy-
properties that empower their use as model compounds of rins’ have attracted attention as potential NLO materials9 and
biological importance and potential material applications.1,2 sensitizers in porphyrin-sensitized solar cells (PSSC).3,10 The
Functionalized porphyrins and their metal complexes were substitution of b-phenylethynyl groups at the porphyrin
employed in dye-sensitized solar cells1d,3 (DSSC), catalysis,4 periphery induces interesting changes in optical absorption and
photodynamic therapy (PDT),5 anion sensing6 and non-linear electrochemical redox properties.11 In general, b-ethynyl linker
optical (NLO) studies7 owing to their unique physicochemical minimizes the steric interaction between the meso-aryl and b-
properties such as high thermal and chemical stability and phenyl groups.11 These planar porphyrins are potential precur-
strong absorption in the visible region. The structural, spectral sors for photochemical or thermal Bergman cyclization reac-
and electrochemical redox properties of porphyrins can be tions.11a,b The distinctive physicochemical properties and
tuned by peripheral functionalization of porphyrin ring.8 potential applications of b-phenylethynyl substituted porphy-
Particularly, the b-functionalization of meso-tetraphenylpor- rins11 prompted us to synthesize and explore the unique prop-
erties of b-tetra- and -octaphenylethynyl substituted porphyrins
and their metal complexes.
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee - 247667,
Herein, we report the facile synthesis, photophysical, electro-
Uttarakhand, India. E-mail: sankafcy@[Link]; Fax: +91-1332-27-3560; Tel: +91-
1332-28-4753 chemical redox, solvatochromism and anion binding properties
† Electronic supplementary information (ESI) available: Fluorescence, 1H NMR of two series of b-phenylethynyl substituted porphyrins viz.
and MALDI-TOF mass spectra, cyclic voltammograms, HOMO–LUMO diagrams, 2,3,12,13-tetrakis(phenylethynyl)-5,10,15,20-tetraphenylporphy-
solvent dependent UV-visible and uorescence spectral proles, UV-Vis spectral rin (H2TPP(PE)4), 2,3,7,8,12,13,17,18-octakis (phenylethynyl)-
titrations of ZnTPP(PE)8 with different anions. See DOI: 10.1039/c5ra15211a

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Scheme 1 Synthetic route to b-phenylethynyl substituted porphyrins.

Chart 1 Chemical structures of b-phenylethynyl substituted

porphyrins.

5,10,15,20-tetraphenylporphyrin (H2TPP(PE)8), and their metal

(Co(II), Ni(II), Cu(II), Zn(II)) complexes (Chart 1). These porphyrins
were characterized by UV-Visible, uorescence, 1H NMR and
mass spectroscopic techniques. To the best of our knowledge,
photophysical, electrochemical redox, solvatochromism, and
anion binding properties of b-tetra- and -octaphenylethynyl
appended meso-tetraphenyl-porphyrins have not been studied so
far.

Fig. 1 UV-Visible absorption spectra of H2TPP(PE)4 and H2TPP(PE)8 in

Results and discussion CH2Cl2.

The precursors, b-bromoporphyrins viz. H2TPPBr4 and

H2TPPBr8 were synthesized using reported procedures.12 exhibited larger red shi in Soret band (Dlmax ¼ 92 nm) and
H2TPP(PE)4 and H2TPP(PE)8 were synthesized in 68–70% yield Qx(0,0) band (Dlmax ¼ 117 nm) as compared to H2TPP sug-
by Stille coupling of H2TPPBr4 or H2TPPBr8 with tribu- gesting that each of the PE group shis 9–11 nm.
tyl(phenyl-ethynyl)stannane in reuxing 1,4-dioxane for 1 hour The observed remarkable red shi both in Soret and Q bands
under argon atmosphere as shown in Scheme 1.11a,11l Notably, was interpreted in terms of extended conjugation by PE groups
we could obtain desired products in lesser time scale (1 hour) as with porphyrin p-system as well as electron withdrawing nature
compared to reported literature.11a,11l Further, Co(II), Cu(II) and of PE substituents.11a,11c
Zn(II) complexes were prepared by reuxing 10 equiv. of The B and Q bands of these porphyrins exhibited an inter-
M(OAc)2$nH2O in CHCl3/MeOH mixture whereas Ni metalation esting trend in red-shi: H2TPP < H2TPP(PE)4 < H2TPP(PE)8.
was carried out by reuxing in DMF with 10 equivalents of The metal complexes exhibited blue-shi in both B and Q bands
Ni(OAc)2$4H2O. 1H NMR and mass spectra of synthesized due to stabilisation of HOMOs.13
porphyrins were shown in Fig. S1–S15 in the ESI.† It is known The synthesized free base and Zn(II) porphyrins were char-
from the literature that MTPP(PE)8 (M ¼ 2H and Zn(II))11a and acterized by uorescence spectroscopy to elucidate the effect of
MT (p-tBu-Ph)P(PE)4 (M ¼ Co(II), Cu(II) and Zn(II))11l exhibited polyphenylethynyl substituents on porphyrin p-system. Fig. 2
planar conformation (Fig. S16 and 17 and Table S1 in the ESI†) represents the steady state emission spectra of H2TPP(PE)4 and
whereas NiTPP(PE)8 showed moderately nonplanar conforma- H2TPP(PE)8. The representative emission spectra of ZnTPP(PE)n
tion due to smaller size of Ni(II) ions and effective bonding of (n ¼ 4, 8) are shown in Fig. S18 in the ESI.† Signicant red
Ni(II) ion with porphyrin nitrogens.11a shied emission (Dlmax ¼ 76–90 nm) was observed for
The optical absorption spectra of H2TPP(PE)4, H2TPP(PE)8 MTPP(PE)8 as compared to MTPP(PE)4. However, weak uo-
and their metal complexes were recorded in CH2Cl2 at 298 K. rescence with feeble uorescence intensities and decreased
Representative absorption spectra of H2TPP(PE)4 and quantum yields were observed for MTPP(PE)8 (M ¼ 2H and
H2TPP(PE)8 are shown in Fig. 1. Table 1 lists the absorption Zn(II)) as compared to MTPP(PE)4 or MTPP (vide infra).
1
spectral data of these porphyrins in CH2Cl2 at 298 K. Free base H NMR spectrum of H2TPP(PE)4 exhibits characteristic
porphyrins exhibited a characteristic Soret band (B band) and resonances arising from b-pyrrole protons, meso-phenyl,
three Q bands whereas metal derivatives exhibited a Soret and b-phenylethynyl (PE) and imino hydrogens (NH) while
two Q bands.8e H2TPP(PE)4 exhibited red shi in B (Dlmax ¼ H2TPP(PE)8 is devoid of b-protons. The ortho protons of meso-
36 nm) and Qx(0,0) (Dlmax ¼ 45 nm) bands whereas H2TPP(PE)8 phenyl of H2TPP(PE)8 are marginally (Dd ¼ 0.17 ppm) downeld

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Table 1 Optical absorption spectral data of synthesised porphyrins in Table 2 Electrochemical redox data of synthesized porphyrins (in V vs.
CH2Cl2 at 298 K. Values in the parenthesis represent log 3 values Ag/AgCl) in CH2Cl2 containing 0.1 M TBAPF6 with a scan rate of 0.1 V
s1 at 298 K
Porphyrin B band, nm Q band(s), nm
Oxidation (V) Reduction (V)
H2TPP(PE)4 453(5.43) 590(4.45), 633(4.11), 692(3.76)
H2TPP(PE)8 507(5.48) 594(4.53), 672(3.99), 764(3.44) Porphyrin I II I II DE (V)
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CoTPP(PE)4 452(5.39) 589(4.35), 622(4.44)

CoTPP(PE)8 496(5.58) 604(4.65), 647(4.47) H2TPP 1.00 1.34 1.23 1.54 2.23
NiTPP(PE)4 457(5.20) 625(4.42) H2TPP(PE)4 1.03 1.21a 0.88 0.98a 1.91
NiTPP(PE)8 497(5.54) 604(4.63), 651(4.47) H2TPP(PE)8 0.99 1.12 0.79 1.06 1.78
CuTPP(PE)4 453(5.36) 574(4.21), 625(4.57) NiTPP 1.02 1.32 1.28 1.72 2.30
CuTPP(PE)8 505(5.50) 618(4.70), 661(4.20) NiTPP(PE)4 1.07 1.25 0.96 1.21 2.03
ZnTPP(PE)4 457(5.50) 579(4.35), 627(4.68) NiTPP(PE)8 1.14 1.25 0.80 1.07 1.94
ZnTPP(PE)8 505(5.47) 619(4.51) CuTPP 0.97 1.35 1.30 1.71a 2.30
CuTPP(PE)4 0.97 1.34 0.95 1.22 1.92
CuTPP(PE)8 0.94 1.46 0.84 1.06 1.78
ZnTPP 0.84 1.14 1.36 1.77 2.20
ZnTPP(PE)4 0.88 1.09 1.18 1.36a 2.06
ZnTPP(PE)8 0.87 1.10 0.92 1.35a 1.79
a
Data obtained from DPV.

Fig. 2 Fluorescence spectra of H2TPP(PE)4 and H2TPP(PE)8 in CH2Cl2

at 298 K.

shied while meta- and para-protons of meso-phenyl and

b-phenyl-ethynyl protons are marginally (Dd ¼ 0.03–0.06 ppm)
upeld shied as compared to H2TPP(PE)4. Notably, the core
imino protons of H2TPP(PE)8 (1.34 ppm) are downeld shied
as compared to H2TPP(PE)4 (2.55 ppm) which are interpreted Fig. 3 Cyclic voltammograms of CuTPP(PE)n (n ¼ 0, 4 and 8) in
CH2Cl2 containing 0.1 M TBAPF6 using Ag/AgCl as reference electrode
in terms of the electron withdrawing and conjugative effect of with a scan rate of 0.1 V s1 at 298 K.
PE groups.11c,11l 1H NMR spectra of MTPP(PE)4 (M ¼ Ni(II) and
Zn(II)) complexes are devoid of imino protons, indicating that
metal got inserted into the porphyrin ring. The meso-phenyl The cyclic voltammograms of CuTPP(PE)n (n ¼ 0, 4 and 8)
proton resonances of MTPP(PE)4 (M ¼ Ni(II) and Zn(II)) are 0.05– complexes are shown in Fig. 3. These porphyrins exhibited two
0.06 ppm upeld shied as compared to corresponding free successive reversible one-electron oxidations and one-electron
base porphyrins. The integrated intensities of proton reso- reductions (Fig. S19, ESI†).14 However, the rst oxidation and
nances of these b-phenylethynyl substituted porphyrins are in rst reduction of Co(II) complexes is a metal centered process
consistent with the proposed structures (Fig. S1–S6, ESI†). which is well documented in literature.14,15
Analysis of electrochemical redox data of MTPP(PE)n (n ¼ 0,
4, and 8; M ¼ 2H, Ni(II), Cu(II), Zn(II)) revealed marginal changes
in rst ring oxidation (10–100 mV) and a drastic anodic shi
Electrochemical redox properties (450–500 mV) in rst ring reduction potential with increase in
To examine the inuence of phenylethynyl (PE) substituents on number of phenylethynyl groups (Fig. 3 and S19, ESI†). The
porphyrin p-system, the electrochemical redox behaviour of anodic shi in rst ring reduction potentials were interpreted in
these porphyrins was studied by cyclic voltammetry in CH2Cl2 at terms of electron withdrawing and conjugative effects of PE
298 K. Under similar conditions, the corresponding MTPP substituents. Similarly, for CoTPP(PE)n (n ¼ 4, 8) complexes, the
derivatives were also examined and the electrochemical redox CoII/III oxidation potentials marginally shied (anodic shi) by
data (vs. Ag/AgCl) is listed in Table 2. 0.06 V while the CoII/I reduction is shied anodically by 0.23–

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nonradiative rate constants (knr) are 2–7 fold higher than

H2TPP. In X-ray structures, the phenylethynyl groups are almost
perpendicular to porphyrin mean plane which indicates some
extent of intramolecular charge transfer must be involved in
ground and singlet excited state resulting into reduced kr and
enhanced knr, poor quantum yields, large Stokes shis and
Published on 23 September 2015. Downloaded by Indian Institute of Technology Roorkee on 02/10/2015 12:40:36.

shortened lifetime values as compared to that of MTPP (Table

3). The photophysical data clearly support the possibility of
intramolecular charge transfer (ICT) from porphyrin core to
phenylethynyl moieties.11c,11k,16 ZnTPP(PE)8 has exhibited large
Stokes shi as compared to other porphyrins in this study due
to the absence of well-dened Qx(0,0) band in the UV-Vis
absorption spectrum.
Fig. 4 Variation of LUMO levels of ZnTPP(PE)4 and ZnTPP(PE)8 in
reference to ZnTPP.
Solvatochromism studies
In order to gain further insight into the photophysical processes
0.49 V as compared to CoTPP14 (Table S2, ESI†). The rst in these compounds, we recorded the absorption and emission
reduction potential of these porphyrins followed the trend 2H > spectra of MTPP(PE)n (M ¼ 2H, Zn(II); n ¼ 0, 4 and 8) in different
Ni(II) > Cu(II) > Zn(II) according to the difference in their elec- solvents and the results are summarized in Table 4 and S3 in the
tronegativity. As we increase the number of phenylethynyl ESI.† The Soret band of H2TPP(PE)8 in various solvents lies
groups, the HOMO–LUMO gap of MTPP(PE)n decreases (0.38– between 506 and 524 nm and is seen to have red-shi with
0.55 V) as compared to MTPP as shown in Fig. 4 and S20, ESI† increasing solvent polarity. This positive solvatochromism17–19
due to extensive stabilization of LUMO. The electrochemical is ascribed to the possibility of charge transfer between the
redox data of these porphyrins clearly indicate the electron electron rich porphyrin core and the electron decient periph-
decient nature of porphyrin p-system.11c eral PE groups. Notably, the b-phenylethynyl substituted
porphyrins have been shown to exhibit charge transfer charac-
Photophysical studies teristics.9a,b,11c The photophysical properties of these porphyrins
are unusual in that they evince considerable charge-transfer
In order to understand the effect of polyphenylethynyl substi- character mixed into the porphyrin B- and Q-type tran-
tution, we have carried out quantum yield and life time sitions9a,b,11c,16 due to p-delocalisation of b-substituent with
measurements. Table 3 lists emission spectral data and the
comparative values of quantum yields, Stokes shis, radiative
(kr) and non-radiative (knr) rate constants of synthesized Table 4 Electronic spectral data of H2TPP(PE)8 in different solvents at
porphyrins. 298 K
MTPP(PE)n (M ¼ 2H, Zn(II); n ¼ 4, 8) exhibit planar confor-
mation as evidenced from their deviation of b-pyrrole carbons Solvent B band, nm Q band(s), nm lem, nm
from the porphyrin mean plane, DCb (0.040–0.094  A) and
Toluene 506(5.52) 593(4.59), 673(3.97), 759(2.61) 810
deviation of 24 core atoms from porphyrin mean plane, D24 DCM 507(5.41) 595(4.48), 672(3.96), 762(3.44) 814
values (0.032–0.068  A) (Table S1, ESI†).11a,11l MTPP(PE)4 and Dioxane 506(5.64) 594(4.68), 672(4.17), 763(3.43) 820
MTPP(PE)8 exhibited decreased uorescence quantum yields THF 504(5.43) 593(4.48), 669(3.96), 760(3.10) 823
and shorter lifetimes than MTPP which is attributed to intra- Pyridine 511(5.45) 597(4.53), 674(4.03), 765(3.22) 826
o-DCB 510(5.47) 595(4.57), 673(4.01), 760(3.32) 809
molecular charge transfer (ICT) from porphyrin core to acceptor
DMF 521(5.30) 605(4.15), 678(3.96) 765
PE moieties.11c,11k,16 The observed radiative rate constants (kr) of DMSO 524(5.20) 691(3.87) 839
MTPP(PE)n are nearly 2–8 times lower than H2TPP whereas

Table 3 Photophysical data of MTPP(PE)n (M ¼ 2H and Zn; n ¼ 0, 4, 8) in CH2Cl2 at 298 Ka

Porphyrin lem, nm Stokes shi (cm1) Ff s (ns) kr (s1) knr (s1) k (s1)

H2TPP 654 718 165 0.11 9.15 1.2  107 9.7  107 1.09  108
H2TPP(PE)4 739 919 9.6  103 1.57 6.1  106 6.3  108 6.37  108
H2TPP(PE)8 814 (w) 804 5.2  103 1.44 3.6  106 6.9  108 6.95  108
ZnTPP 598 644 372 3.0  102 1.59 1.9  107 6.4  108 6.62  108
ZnTPP(PE)4 644 421 1.9  102 0.55 3.4  107 1.8  109 1.81  109
ZnTPP(PE)8 736 (w) 2568 2.3  103 0.97 2.4  106 1.0  109 1.02  109
a
W ¼ weak emission intensity.

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porphyrin p-system. This is further supported by the increased to 1.6 ns) (Table S4, ESI†).17 To investigate further sol-
bandwidth of the Soret band (B band) of H2TPP(PE)8 (FWHM ¼ vatochromism behaviour of PE groups, we recorded the uo-
49 nm) and ZnTPP(PE)8 (FWHM ¼ 36 nm) with respect to H2TPP rescence life time decay and analysed using a multi exponential
(FWHM ¼ 14 nm) and ZnTPP (FWHM ¼ 11 nm).16 Furthermore, decay. In more polar solvents, H2TPP(PE)8 and ZnTPP(PE)8
the possibility of deprotonation by various solvents listed in exhibited di- or triexponential uorescence decay, this is may be
Table 4 is ignored as the UV-Vis spectral proles of deproto- due to the emission of porphyrin core is partially quenched by
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nated H2TPP(PE)8 is completely different as that of solvent the acceptor PE moieties. We observed almost linear t between
dependent proles (Fig. S21, ESI†). The absorption spectra of Stokes shi of H2TPP(PE)8 in different solvents and dielectric
H2TPP(PE)4 are nearly independent of solvent polarity and constant which indicates enhanced charge transfer in polar
shows no appreciable colour change in different solvents solvents (Fig. S24a and b in ESI†). The solvent induced changes
(Fig. S22, ESI†) with marginal shi (2–7 nm) which indicates were examined according to the Lippert–Mataga method.22
weak intramolecular interaction between donor and acceptor According to this method, the plot between the observed Stokes
groups in the ground state. Notably, ZnTPP(PE)4 and shi (nst) and solvent orientation polarizability (Df) must be
ZnTPP(PE)8 exhibit 13–18 nm shi in their Soret band while linear for simple solvent–solute interactions whereas nonlinear
increasing solvent polarity from toluene to DMSO. However, t will be observed in case of solvent–solute interactions asso-
there is no regular trend observed with solvent polarities in ciated with charge transfer (CT) and hydrogen bonding inter-
Zn(II) complexes which is due to combined solvatochromism actions.22 In case of H2TPP(PE)8, we observed nonlinear t
arising from axial ligation of coordinating solvents and intra- indicating charge transfer interactions mixed into the p–p*
molecular interaction between donor (porphyrin core) and transitions. While ZnTPP(PE)8 exhibited more scattered points
acceptor (PE) groups in the ground state (Fig. S23, ESI†).19 In due to the combined effect of charge transfer and axial ligation
pyridine, a highly red-shied absorption spectrum was (Fig. S24c and d in ESI†).20
observed for Zn(II) complexes which is probably due to the
strong axial coordination of pyridine to the zinc metal centre.20 Anion binding studies
A distinctive bathochromic shi (20–30 nm) in emission band
A wide variety of porphyrinoids6 and organic sensors23 were
was also observed (Fig. 5 and S23, ESI†) for free bases and Zn(II)
utilised for sensing of toxic anions. A qualitative assessment of
complexes as we move from less polar solvent (toluene) to more
colorimetric responses of MTPP(PE)n (M ¼ 2H, Zn and n ¼ 4, 8)
polar solvent (DMSO) along with successive decrease in uo-
to various anions have also been carried out in CH2Cl2 at 298 K
rescence intensity. H2TPP(PE)4 exhibits broad structureless
with various anions in the form of TBA salts.
weak emission in high polar solvents like DMF and DMSO.
H2TPP(PE)8 selectively interacts with F and CN ions which
These results suggests an internal charge transfer which results
are reected by red-shied UV-Visible spectra with colorimetric
from stabilization of polar excited state by polar solvents and is
‘naked eye’ sensing of F and CN ions (reddish brown to dark
well documented with donor–acceptor uorophores.17–19,21
pink) whereas no observable shi was found with other tested
H2TPP(PE)8 exhibited blue shied emission (negative sol-
anions as shown in Fig. 6. These anions show sensing via anion
vatochromism) in DMF. This is possibly due to less stable and
induced deprotonation mechanism as the UV-Visible spectral
less polar excited state than the ground state which is further
proles obtained for H2TPP(PE)8 with F and CN resemble the
supported by the lower life time (0.66 ns) as compared to other
solvents such as CH2Cl2, toluene, THF and dioxane (life time 1.3

Fig. 5 (Top) colorimetric response of H2TPP(PE)8 in different solvents; Fig. 6 (Top) colorimetric response of H2TPP(PE)8 with tested anions in
(bottom) UV Visible and fluorescence spectra of H2TPP(PE)8 in CH2Cl2; (bottom) UV-Vis spectra of H2TPP(PE)8 upon addition of
different solvents at 298 K. excess of TBA salts of tested anions in CH2Cl2 at 298 K.

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optical absorption spectrum obtained by the addition of TBAOH Table 5 Optical absorption data of ZnTPP(PE)8 (1) in presence of
(Fig. S21, ESI†). Further, we have recorded the 1H NMR of different anions in CH2Cl2 at 298 Ka
H2TPP(PE)8 in presence of CN and F ions in CDCl3 at 298 K.
Porphyrin B band, nm Q band(s), nm DB, nm DQ, nm
The disappearance of NH signal and cathodic shi in redox
potentials conrm the anion induced deprotonation mecha- 1 505(5.52) 622(4.54) — —
nism as shown in Fig. S25a and S26 in the ESI.† 1 + CN 537(5.43) 672(4.38) 32 50
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The anionic species formed aer deprotonation have stronger 1 + F 528(5.44) 654(4.32) 23 32
1 + Cl 535(5.41) 665(4.29) 30 43
hydrogen bonding with protonated anion (HCN or HF) which 1 + Br 505(5.39), 533(sh) 622(4.0), 648(sh) 0 0
leads to large spectral shi.24 While using TBAOH, the formed 1 + OAc 528(5.42) 652(4.37) 23 30
anionic species and water are in equilibrium with reactant 1 + H2PO4 524(5.37) 646(4.34) 19 24
(H2TPP(PE)8) possibly due to weaker hydrogen bonding inter- a
DB ¼ Shi in B band w.r.t ZnTPP(PE)8 (1); DQ ¼ Shi in Q band w.r.t
actions (Fig. S25b, ESI†). Interestingly, H2TPP(PE)4 doesn't show ZnTPP(PE)8 (1).
any UV-Vis spectral change and colorimetric response even
towards highly basic anions like F and CN (Fig. S27, ESI†).
Notably, ZnTPP(PE)8 is able to sense F, Cl, Br, CN, CH3-
COO and H2PO4 ions which have shown considerable red-
shis in Soret (Dlmax ¼ 19–32 nm) and Q bands (Dlmax ¼ 30–50
nm) in CH2Cl2. Fig. 7 represent the colorimetric ‘naked eye’
sensing of these anions by ZnTPP(PE)8. Table 5 and S5† list the
UV-Vis spectral data of ZnTPP(PE)8, H2TPP(PE)8 and ZnTPP(PE)4
in presence of different anions in CH2Cl2 at 298 K. The shi in B
and Q bands are in accordance with the basicities of anions (pKa)
except Cl ion due to effective CT from chloride ion to porphyrin
than F ion. No observable UV-Vis shis and observable colour
changes are observed with I, NO3, ClO4 and HSO4 ions.

Axial ligation studies

UV-Vis titrations were carried for ZnTPP(PE)n with basic anions
in order to measure binding constants and stoichiometry of Fig. 8 UV-Vis titration of ZnTPP(PE)8 (4 mM) while increasing the
complexation.20 Fig. 8 represents the UV-Vis spectral titration of concentration of cyanide ions (6–47.5 mM) in toluene at 298 K. Inset
ZnTPP(PE)8 with CN ions in toluene at 298 K. Both the Soret shows the corresponding Hill plot.
(Dlmax ¼ 32 nm) and Q bands (Dlmax ¼ 50 nm) are red shied
upon increasing the concentration of TBACN indicating the
axial coordination of CN ions to ZnTPP(PE)8 with well- CH3COO and H2PO4 ions. Fig. S28 and S29 in the ESI†
anchored isosbestic points at 462, 521, 554 and 645 nm during represent the UV-Vis titration of ZnTPP(PE)8 with Cl, CH3-
the course of CN ion binding experiment. Similar, UV-Vis COO, ions and ZnTPP(PE)4 with CN ions, respectively in
spectral proles were observed for ZnTPP(PE)8 with F, Cl, toluene at 298 K. The binding constants were calculated using
Hill equation25 and the corresponding binding data are pre-
sented in Table 6. The binding constants are increasing as the
basicity of anion increases except for Cl and F ions. The
higher binding constant was observed for Cl ions as compared
to F ions with ZnTPP(PE)8 is possibly due to effective charge
transfer from Cl ion to Zn(II) metal center. It is known from the
literature that Cl binds effectively with Zn(II) porphyrins as

Table 6 Binding constant data of ZnTPP(PE)n with anions in toluene at

298 K and n represents the stoichiometry of complexation

Porphyrin Anion b2 (M2) log b2 n

ZnTPP(PE)8 CN 1.26  1012 12.10 2.5

Cl 8.71  1011 11.94 2.3
CH3COO 2.09  109 9.32 1.7
H2PO4 3.98  107 7.60 1.8
Fig. 7 (Top) colorimetric response of ZnTPP(PE)8 with tested anions in F 8.13  106 6.91 1.7
CH2Cl2; (bottom) UV-Vis spectra of ZnTPP(PE)8 upon addition of F ZnTPP(PE)4 CN 2.69  109 9.43 2.1
and CN ions in the form of TBA salts in CH2Cl2 at 298 K.

82242 | RSC Adv., 2015, 5, 82237–82246 This journal is © The Royal Society of Chemistry 2015
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compared to Br and I anions according to their basicity.20a,e,f Instrumentation and methods
The stoichiometry of complexation was conrmed by Hill plot25
UV-Vis absorption spectra were measured in distilled
(Fig. 8 inset and Table 6). The Hill plot shows a straight line
dichloromethane or toluene using Agilent Cary 100 spectro-
between log[CN] and log(Ai  A0/Af  Ai) having slope value 2,
photometer with a pair of quartz cells of 10 mm path length and
which indicates 1 : 2 (porphyrin-to-cyanide) stoichiometry.
the uorescence spectra were recorded on Hitachi F-4600
These results clearly reveal enhanced the Lewis acidic nature of
spectrouorometer using a quartz cell of 10 mm path length. 1H
Published on 23 September 2015. Downloaded by Indian Institute of Technology Roorkee on 02/10/2015 12:40:36.

Zn(II) center due to electron withdrawing nature of polyphen

NMR spectra were recorded on Bruker AVANCE 500 MHz and
ethynyl groups. To the best of our knowledge, this is rst report JEOL ECX 400 MHz spectrometers using CDCl3 as a solvent.
on Zn(II) porphyrins20 showing very high binding constants MALDI-TOF-MS spectra were measured using a Bruker Ultra-
(1012 to 107 M2) with anions as compared to ZnTPP.20a
eXtreme-TN MALDI-TOF/TOF spectrometer using HABA as a
matrix. Electrochemical measurements were carried out using
CHI 620E electrochemical workstation. A three electrode
Conclusions assembly was used consisting of a Pt disk working electrode, Ag/
AgCl as a reference electrode and a Pt-wire as a counter elec-
Phenylethynyl-substituted porphyrins were synthesized by Stille
trode. These cyclic voltammetric studies were carried out under
coupling reaction in shorter timescale as compared to literature Ar atmosphere. Fluorescence life time measurements in ns time
methods. H2TPP(PE)8 exhibited red shi of 92 nm in Soret and domain were recorded in CH2Cl2 using Horiba Jobin Yvon
117 nm in longest wavelength, Qx(0,0) bands as compared to “uorocube uorescence life time system” equipped with
H2TPP. MTPP(PE)n exhibited only marginal shi in rst oxida- NanoLED (635 nm) source. The binding constants were calcu-
tion potentials (10–100 mV) whereas profound anodic shis
lated using Hill equation.25
were found in the rst ring reduction potentials (DEred ¼ 450–
500 mV), which are interpreted in terms of electron withdrawing
General procedure for the synthesis of b-tetra- or
and conjugative effect of phenylethynyl substituents. Hence, we
octaphenylethynyl substituted meso-tetraphenylporphyrins
could observe substantial decrement in the HOMO–LUMO gap.
The free base and Zn(II) porphyrins exhibited lower uorescence H2TPPBr4 or H2TPPBr812 (0.108 mmol) and Pd(PPh3)4 (20 mol%)
quantum yields and lifetime values as compared to MTPPs. were dissolved in 50 mL of distilled 1,4-dioxane and purged with
MTPP(PE)8 display a strong solvatochromism which is reected Ar gas for 15 minutes. To this, tributyl(phenylethynyl)-stannane
by a large red-shi in their absorption and emission maxima (10 equiv. for H2TPPBr4 and 20 equiv. for H2TPPBr8) in 10 mL of
while increasing the solvent polarity. These porphyrins exhibi- degassed dioxane was added and heated to 80  C for 1 hour
ted lower radiative rate constants (kr) and enhanced non- under Ar atmosphere. Aer completion of the reaction, the
radiative rate constants (knr) as compared to MTPP. The solvent was removed by vacuum distillation. The crude
decrement in uorescence lifetime values, quantum yields, porphyrin was redissolved in CHCl3 (20 mL) and puried on
radiative rate constants (kr) and profound solvatochromism silica column using CHCl3/hexane mixture (7 : 3, v/v) to 100%
with enhanced nonradiative rate constants (knr) have been CHCl3 as eluent. The desired products were recrystallized from
interpreted in terms of intramolecular charge transfer (ICT) CHCl3/CH3OH mixture (1 : 3, v/v). Yields were found to be 68%
from porphyrin core to phenylethynyl moieties associated with and 70% for b-tetra- and octa-phenylethynyl substituted
extended p-conjugation. Further, ZnTPP(PE)8 was utilized for porphyrins, respectively.
the colorimetric “naked-eye” sensing of CN, F, Cl, Br,
H2PO4 and CH3COO ions through axial coordination of 2,3,12,13-tetra(phenylethynyl)-5,10,15,20-tetraphenyl
anion to Zn(II) metal centre. The enhanced Lewis acidity of porphyrin, (H2TPP(PE)4)
ZnTPP(PE)8 is further proved by axial ligation studies. Further-
Yield ¼ 68%; UV/Vis (CH2Cl2): lmax (nm) (log 3) 453 (5.43), 544
more, ZnTPP(PE)8 exhibited extremely high binding constants
(4.32), 590 (4.45), 632 (4.11); 1H NMR (400 MHz, CDCl3) d (ppm)
(1012 to 107 M2) with anions as compared to ZnTPP.
8.71 (s, 4H, b-pyrrole-H), 8.25 (d, 8H, J ¼ 6.5 Hz, meso-o-phenyl-
H), 7.80–7.69 (m, 12H, meso-m- and p-phenyl-H), 7.36–7.33 (m,
8H, b-pyrrole-o-PE-H), 7.29–7.26 (m, 12H, b-pyrrole-m- and p-PE-
Experimental section H), 2.55 (s, 2H, imino-H). MALDI-TOF-MS (m/z): found
Chemicals and materials 1016.44 [M + H]+, calcd 1016.24. Anal. calcd for C76H46N4: C,
89.91; H, 4.57; N, 5.52. Found: C, 89.73; H, 4.64; N, 5.61.
All the reagents employed in the present work were purchased
from Sigma Aldrich and used as received without further puri-
cation. All solvents employed in the present work were of 2,3,7,8,12,13,17,18-octa(phenylethynyl)-5,10,15,20-
analytical grade and distilled or dried before use. Silica gel (100– tetraphenyl-porphyrin (H2TPP(PE)8)
200 mesh) used for column chromatography was purchased Yield ¼ 70%; UV/Vis (CH2Cl2): lmax (nm) (log 3) 507 (5.48), 590
from Rankem and used as received. The tetrabutylammonium (4.45), 633 (4.11), 692 (3.76); 1H NMR (500 MHz, CDCl3) d (ppm):
salts (TBAX, X ¼ CN, F, Cl, Br, I, HSO4, OAc, H2PO4, 8.42 (d, 8H, J ¼ 7.5 Hz, meso-o-phenyl-H), 7.77 (t, 8H, J ¼ 7.5 Hz,
ClO4, PF6 and NO3) used for sensing applications were meso-m-phenyl-H), 7.65 (t, 4H, J ¼ 7.5 Hz, meso-p-phenyl-H), 7.29
purchased from Alfa Aesar and used as received. (d, 16H, J ¼ 7.3 Hz, b-pyrrole-o-PE-H), 7.26–7.20 (m, 24H, b-

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RSC Advances Paper

pyrrole-H, m- and p-PE-H), 1.34 (s, 2H, imino-H). MALDI-TOF- CoTPP(PE)8. Yield ¼ 91%; UV/Vis (CH2Cl2): lmax (nm) (log 3)
MS (m/z): found 1417.15 [M + H]+, calcd 1417.72. Anal. calcd for 496 (5.58), 604 (4.65), 647 (4.47); MALDI-TOF-MS (m/z): found
C108H62N4: C, 91.63; H, 4.41; N, 3.96. Found: C, 91.55; H, 4.60; N, 1473.18 [M + H]+, calcd 1473.63. Anal. calcd for C108H60N4Co: C,
3.72. 88.09; H, 4.11; N, 3.80. Found: C, 87.96; H, 4.04; N, 3.97.
CuTPP(PE)8. Yield ¼ 94%; UV/Vis (CH2Cl2): lmax (nm) (log 3)
505 (5.50), 618 (4.70), 661 (4.20); MALDI-TOF-MS (m/z): found
Published on 23 September 2015. Downloaded by Indian Institute of Technology Roorkee on 02/10/2015 12:40:36.

Synthesis of Co(II), Ni(II), Cu(II) and Zn(II) complexes 1478.06 [M + H]+, calcd 1478.24.
Corresponding free base porphyrins viz. H2TPP(PE)4 or
H2TPP(PE)8 (0.02 mmol) was dissolved in 15 mL of CHCl3. To Acknowledgements
this, 10 equiv. of M(OAc)2$nH2O (M ¼ Co(II), Cu(II) and Zn(II)) in
2 mL of methanol was added and reuxed on water bath for 50 We are grateful for the nancial support provided by Council of
minutes. The solvent was then evaporated to dryness and Scientic and Industrial Research (01(2694)/12/EMR-II), Science
redissolved in minimum amount of CHCl3 and washed with and Engineering Research Board (SB/FT/CS-015/2012) and
water (2  15 mL). The crude product was puried by column Board of Research in Nuclear Science (2012/37C/61/BRNS/2776).
chromatography on silica column using CHCl3 as eluent. Yields RK sincerely thanks Ministry of Human Resource development
were found to be 85–90%. Further, Ni(II) complexes were (MHRD) for fellowship. PY and PR thank Council of Scientic
prepared by reuxing free bases and Ni(OAc)2$2H2O (10 equiv.) and Industrial Research (CSIR), India for fellowship.
in DMF for 2 hours under Ar atmosphere followed by the
precipitation with water. The crude product was puried on Notes and references
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