Materials Letters 200 (2017) 69

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Materials Letters
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Novel iridium-pentafluorophenyl porphyrin complex

Ana Delgado-Lima a,, Antnio M. Fonseca b, Ana V. Machado a
a
Institute for Polymers and Composites/I3N, University of Minho, Azurm, 4800-0581 Guimares, Portugal
b
Department of Chemistry, University of Minho, Campus de Gualtar, 4710-057 Braga, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: The novel iridium-pentafluorophenyl porphyrin complex (TPFPPIrCl(CO)) was successfully synthesized
Received 31 July 2016 by chemical reaction with the iridium (I) metal precursor [Ir(COD)Cl]2. The final complex was identified
Received in revised form 24 March 2017 linked to the axial Cl and CO ligands by UVVisible, 1H, 13C NMR spectroscopy as well the 1H/13C corre-
Accepted 30 March 2017
lated techniques and by mass spectrometry.
Available online 4 April 2017
2017 Published by Elsevier B.V.

Keywords:
Coordination chemistry
Synthesis
Porphyrins
Iridium
Spectroscopy

1. Introduction has attractive properties, such as, high melting point, chemical sta-
bility, superior oxidation resistance and high electrical resistivity.
Porphyrins are an important class of compounds directly Which makes iridium complexes promising materials for a wide
involved in biological phenomena, but also in other very appealing range of applications from heavy-metal-ion sensors, catalysis and
applications, such as, as reaction catalyst and photosensitizers in switching layers in electrochromic devices [1321]. Although irid-
photodynamic therapy, molecular electronic devices and solar ium has been successfully employed in the preparation of
energy conversion [111]. These macromolecules derive from por- cyclometalated compounds [2226] with remarkable photophysi-
phin and consists of aromatic macrocycles of four pyrrole rings, cal and photochemical properties with applications in important
which are substituted at b and/or meso positions linked by a fields, such as organic emitting diodes (OLEDs), dyes sensitizing
methine bridge [1,2,5,11]. Porphyrins are also very attractive mole- solar cells, sensors, biology and photocatalysis, only a few exam-
cules due to their capability of forming complexes with most of the ples can be found in the literature about its incorporation in por-
elements in the periodic system, by the loss of the two inner NH phyrins [2731]. Therefore, the synthesis of iridium porphyrins
protons and further metal coordination, showing distinctive prop- complexes would be of great scientific and technological impor-
erties from the porphyrin initial precursor [6,12,13]. In the case of a tance. The pentafluorophenyl substituted porphyrin (TPFPP),
favored octahedral geometry by the metal ion, the porphyrin coor- which is oxidatively more robust and has better solubility in com-
dination sphere is normally completed with ligands [11]. It is also mon organic solvents than its phenyl analogue, is a promising can-
of great importance to mention that the facility of coordination of a didate [14]. The substitution of hydrogen terminated species by
metal ion with a porphyrin depends mainly on the available space fluorine atoms are known to turn possible the electronic transport
between the porphyrin core (approximately radius = 7590 pm), properties to switch from a p- to a n- type, making this porphyrin
and the ionic radius of the metal ion. Therefore, there does not of particular relevance and a capable candidate for thin film based
exist a single metal insertion procedure that can be applied to all electronic devices [32]. Gas sensor is also a suitable application,
metals and porphyrins [5,6,11,12]. And while for 3d metals, the since TPFPP coordinated with Zn atoms have demonstrated a sig-
ionic radius matches the available space of the porphyrin core, nificant enhancement in gas-response of ammonia-sensing [15].
resulting in a planar geometry with the porphyrin [12]. For larger Moreover, the TPFPP is an appropriate platform to several substitu-
ions coordination, 4d and 5d, the metal ion is usually positioned tions, once the pentafluorophenyl group of the porphyrin is not a
outsite the porphyrin plane [5]. Iridium, a 5d9 transition metal, chemically inert group, suffering aromatic nucleophilic substitu-
tions with a range of nucleophiles (RO-, RNH2, RS) [14,1623].
Corresponding author. For example, Samaroo et al. [16] showed the efficacy of using
E-mail address: [email protected] (A. Delgado-Lima).
TPFPP as a core platform to obtain porphyrins bearing

http://dx.doi.org/10.1016/j.matlet.2017.03.177
0167-577X/ 2017 Published by Elsevier B.V.
 A. Delgado-Lima et al. / Materials Letters 200 (2017) 69 7

functionalities that are important to photodynamic therapeutics silica gel with a mixture of nhexane/dichloromethane and it
(PDT) and that can be used for noble purposes as treatment for was isolated in 5% yield. Found in 1H NMR (400 MHz, CDCl3,
cancer or as a potential antibacterial or antiviral compound [16]. 25 C) d ppm: 9.02 (s, 8H, bH-pyrrole). And 13C NMR (400 MHz,
CDCl3, 25 C) d ppm: 105.98 (C5,10,15,20), 128.98 (C2,3,7,8,12,13,17,18),
2. Material and methods 141.52 (C1,4,6,9,11,14,16,19), 119.84 (Cp) UVVis (CH2Cl2) k abs nm:
413.5 (1E105 M
1cm
1), 526.0 (1.5E104 M
1cm
1), 557.5 (5E103
The porphyrin 5,10,15,20-tetrakis(pentafluorophenyl)por M
1cm
1). ESI-MS: C45H8ClF20IrN4NaO m/z = 1250.96.
phyrin (TPFPP) (98%purity) was purchased from SigmaAldrich.
Reagents and solvents, namely chloro(1,5-cyclooctadiene)iridium 3. Results and discussion
(I) dimer ([Ir(COD)Cl]2) (97% purity) was purchased from Sigma
Aldrich, xylene, dichloromethane and nhexane were purchased As mentioned, TPFPP is a porphyrin of huge interest and it is
from Acros Organics and used without further purification. Thin used on the research of new materials to be employed in a wide
layer chromatography was performed in Merck pre-coated silica range of applications [2426,3243]. Therefore, combining the
gel 60 F-254 plates and silica gel 60 M (0.040.063 mm) from attractive properties of TPFPP with the iridium metal by the
MachereyNagel was used for column chromatography. All the synthesis of a porphyrin complex became a great challenge. The
compounds were characterized by 1H and 13C NMR spectroscopy, experimental firsts attempts in our laboratory were performed in
including 1H/13C correlation techniques, which were recorded on IrCl4 without reaction success. Similarly, to the iridium coordina-
a Bruker Avance III, 400 MHz in deutered CHCl3. The spectra were tion in other porphyrins procedure, the dimer [IrI(COD)Cl]2
internally referenced to the residual proton tetramethylsilane (COD = cyclooctadiene) was used as the metal precursor [28
(TMS, d = 0.00 ppm) and the chemical shifts (d) are reported as part 31,44]. Since iridium is a six-coordinated atom, CO and Cl axial
per million (ppm). Absorption spectra were measured at a Shi- ligands neutralize the molecule and complete the coordination
madzu UV-2401PC UVVis spectrophotometer in CH2Cl2 in a range sphere (Fig. 1). The first experiments were performed in smoother
between 300 and 700 nm, and mass spectrometry (ESI) was per- solvents, as acetone and pyridine, but no reaction evolution was
formed on an APEXQe FT-ICR MS (Bruker Daltonics, Billerica, detected. Clearly, the solvent selection was of major relevance
MA), equipped with a 7T actively shielded magnet. Ions were gen- and higher boiling temperatures were preferable [5]. Also, the
erated using a Combi MALDI-electrospray ionization (ESI) source. coordination ability of the solvent by the presence of lone pairs
Ionization was achieved by electrospray, using a voltage of 4500 or electron-rich donor atoms might affect the reaction, avoiding
V applied to the needle, and a counter voltage of 300 V applied the coordination of the metal in the porphyrin. Thus, the iridium
to the capillary. Samples were prepared by adding a spray solution porphyrin (TPFPPIrCl(CO)) was only successfully obtained after a
of 70:29.9:0.1 (v/v/v) CH3OH/water/formic acid or 70:29.9:0.1 (v/v/ 4-day reaction in reflux using a high boiling point and non-
v) CH3CN/water/formic acid to a solution of the sample at a v/v coordinating solvent, xylene. Despite the success of this reaction,
ratio of 1 to 5 % to give the best signal-to-noise ratio. Data acquisi- the yield of 5% demonstrates that it is difficult to incorporate a
tion was performed using the ApexControl software version 3.0.0, large metal atom in sterically hindered porphyrins. The iridium
and data processing was performed using the DataAnalysis soft- porphyrin complex was isolated and its presence was confirmed
ware, version 4.0 both from Bruker Daltonics. Supplementary data by spectroscopy and spectrometry techniques. Fig. 2 presents the
are given as electronic Supplementary material. UVVis spectra of porphyrin TPFPP and metallated TPFPPIrCl(CO).
The spectrum of porphyrin shows two p-p electronic transitions.
2.1. Synthesis of the TPFPP metalloporphyrin An intense Soret band between 350500 nm with molar absorptiv-
ities (e) of 105 M
1cm
1, and four lower intense (e  104
101 M
1-
The TPFPPIrCl(CO) metalloporphyrin was synthesized by adding cm
1) Q-bands between 500750 nm as a result of the presence of
the dimer [Ir(COD)Cl]2 (261.9 mg, 0.39 mmol) to a solution of free- protons on two diagonally situated pyrrole nitrogen [5,43,45]. The
base porphyrin (246.9 mg, 0.26 mmol) in xylene ([C] = 6.5E
3 M) coordination of iridium with the porphyrin core induces significant
(Fig. 1). The resulting mixture was refluxed for 4 days and allowed changes in the UVVis spectrum. Specifically, the main difference
to cool to room temperature followed by solvent evaporation to consists in the 2 Q-bands of the metalloporphyrin with displaced
dryness. The residue was purified by column chromatography on wavelengths, which also reveals the existence of axial ligands by

Fig. 1. Scheme reaction of TPFPP metallation with iridium.

8 A. Delgado-Lima et al. / Materials Letters 200 (2017) 69

bonds of TPFPP at d(ppm) 135150, which were probably covered

by the background noise on the metallated porphyrin spectrum.
The iridium porphyrin complex identification was confirmed by
ESI-MS in the presence of Na+ with a correspondent mass of
1250.96 g/mol, in agreement with the theoretical mass of
1251.14 g/mol.

4. Conclusions

A novel iridium-pentafluorophenyl porphyrin complex

(TPFPPIrCl(CO)) was successfully synthesized. The iridium center
metal was stabilized with Cl and CO ligands, which completed
the coordination sphere. The reaction was enhanced at higher boil-
ing temperatures, in the absence of solvents or other compounds
with lone pairs of electrons or electron-rich donors that avoid
the metallation reaction. As future work, the reaction conditions
and compound separation will be optimized to increase the reac-
tion yield and to exploit the capacities of this new compound in
Fig. 2. UVVis spectra of TPFPP and metallated TPFPPIrCl(CO). The inset is a
several applications.
magnified view of the UV range of the Q-bands (450650 nm).

Acknowledgements
the difference between the more intense Q(0,0) band at 526.0 nm
and the less intense Q(1,0) band at 557.5 nm [5]. The formation The authors acknowledge the Portuguese Foundation for
of dimers and higher aggregates was not observed, since red or Science and Technology (SFRH/BD/81711/2011 and PEst-C/CTM/
blue shifts and broadening of the Soret band were not detected LA0025/2011) and n-STeP Nanostructured systems for Tailored
[4648]. Properties with reference NORTE-07-0124-FEDER-000039, sup-
The NMR spectrum of the commercial TPFPP is in agreement ported by the Programa Operacional Regional do Norte (ON.2).
with literature [49], where the pyrrole protons are identified at
negative chemical deviations of d(ppm)
2.87 (s, 2H, NH) due to Appendix A. Supplementary data
the shielding effect promoted by the association of ring currents
with the p-system of the aromatic macrocycle [50]. The deshield- Supplementary data associated with this article can be found, in
ing of the peripheral protons that are presented at 8.96 ppm the online version, at http://dx.doi.org/10.1016/j.matlet.2017.03.177.
respectively (d, 8H, bH-pyrrole) is also a consequence of the previ-
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