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Dual emission and multi-stimuli-response in

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iridium(III) complexes with aggregation-induced

Cite this: J. Mater. Chem. C, 2017,
enhanced emission: applications for quantitative
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5, 7784

CO2 detection†
Clàudia Climent,‡a Parvej Alam,‡b Sheik Saleem Pasha,b Gurpreet Kaur,c
Angshuman Roy Choudhury,c Inamur Rahaman Laskar, *b Pere Alemany *a
and David Casanova *de

Four new Ir(III) complexes with the general formula [IrHCl(C^N)(PPh3)2] containing different conjugated
Schiff base ligands (C^N) have been synthesized and characterized by 1H, 13
C, and 31
P NMR, HRMS, and
IR spectra and one of them by single crystal X-ray diffraction. Their photophysical properties in solution
and in the solid state have been analyzed and three main practical results have been obtained: (i) a dual
Received 22nd May 2017, fluorescent and phosphorescent emissive complex in solution, (ii) successful acid/base sensing in the
Accepted 6th July 2017 solid state and (iii) quantitative CO2 detection. Quantum chemical calculations have been employed to
DOI: 10.1039/c7tc02250f assign the character of the lowest excited states. A plausible explanation for the observed aggregation
induced enhanced emission (AIEE) is given, based on the restriction of intramolecular motions due to
[Link]/materials-c the effect of intermolecular C–H


p and C–H


Cl type interactions upon aggregation.

1. Introduction makes them appealing for applications such as solid state

lighting, where the luminescent complexes are present in
Ir(III) complexes with long luminescence lifetimes (from 100 ns aggregated forms such as solids or thin films. A key step in
to ms), large Stokes shifts, high quantum yields and versatile developing new materials based on the AIEE effect is to under-
color tuning by modification of the coordinating ligands are stand its origin at a fundamental level. The mechanism behind
renowned as phosphorescent materials for their potential AIEE is, however, still under debate29–32 since many types of
applications in the fields of organic light-emitting diodes different systems, ranging from purely organic molecules
(OLEDs),1–3 photoredox catalysis,4 vapoluminescent materials5–7 to organometallic complexes, sometimes containing highly
or luminescent probes for biological systems.8–10 flexible parts, but in other cases quite rigid, have been identified
In the last decade, several studies have demonstrated Ir(III) as AIEE active compounds. In order to understand the origin of
compounds to be excellent candidates for materials exhibiting this photophysical phenomenon and identify the key parameters
‘Aggregation-Induced Enhanced Emission’ (AIEE),11–28 which controlling its efficiency to optimize the implementation of
AIEE materials in technological applications, it is necessary
a
to combine experimental investigations with theoretical and
Departament de Ciència de Materials i Quı́mica Fı́sica and Institut de Quı́mica
Teòrica i Computacional (IQTCUB), Universitat de Barcelona,
computational studies.
Martı́ i Franquès 1-11, Barcelona 08028, Spain In the present work, we report the complete synthesis of four
b
Department of Chemistry, Birla Institute of Technology and Science, Pilani novel Ir(III) complexes (1–4) by aliphatic C–H activation of a
Campus, Pilani, Rajasthan, India Schiff base ligand, in line with recent reports on the synthesis
c
Department of Chemical Sciences, Indian Institute of Science Education and
of new Ir(III)11,19–21,33–37 and Pt(II)38 luminescent complexes.
Research (IISER), Sector 81, S. A. S. Nagar, Manauli PO, Mohali, Punjab, 140306,
India
Using both experimental characterization techniques and ab initio
d
Kimika Facultatea, Euskal Herriko Unibertsitatea (UPV/EHU), Donostia quantum chemical calculations we explore the photophysical
International Physics Center (DIPC), Paseo Manuel de Lardizabal, 4, properties of the synthesized compounds. In particular, complex
Donostia 20018, Spain. E-mail: [Link]@[Link] 4 has been found to exhibit dual fluorescence and phosphores-
e
IKERBASQUE, Basque Foundation for Science, Bilbao 48013, Spain
cence emission with the particularity that the fluorescent
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c7tc02250f
emission band is solvatochromic. This property is indeed
‡ Both authors contributed equally to this work, C.C with the computational part very suitable for the development of Ir(III) probes,39 in which
and P.A with the experimental one. switching of the luminescence by external stimuli is essential.

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In the literature, there are several examples of dual phosphorescent ether followed by ethanol for several times to obtain a solid
Ir(III) complexes,40–47 but dual fluorescent and phosphorescent Ir(III) (60–70%) of 1–4 that was further purified through recrystalliza-
complexes are still scarce.48–51 To the best of our knowledge, tion from a mixture of DCM and hexane (1 : 1). X-ray quality
the Ir(III) complex that we report herein is the first example of single crystals could only be obtained for complex 2. Single
facile emission tuning between a singlet and a triplet state by crystal X-ray diffraction (SCXRD) revealed that the one-pot
just varying the solvent’s polarity. This certainly opens a whole reaction of Ir(III) chloride and the triphenylphosphine mixture
new range of possibilities for the application of Ir(III) complexes with the Schiff base resulted in a structure in which the imine
as luminescent probes. C–H position was activated by Ir(III).
The capability of the synthesized complexes as acid–base
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sensors in the solid state and the potential use of complex 4 in 2.3 Characterization
1
the quantitative detection of CO2 has also been explored. Due to H, C and 31P NMR spectra were recorded in a 400 MHz
13
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the well-known harmful effects that high concentrations of CO2 Bruker spectrometer using CDCl3 as a solvent. Tetramethyl-
have on human beings, the development of molecular sensors silane (TMS, d = 0 for 1H and 13C NMR) and phosphoric acid
for its quantitative detection is nowadays an intense research (H3PO4, d = 0 for 31P NMR) were used as internal standards.
field.52–58 Current detection techniques59,60 based on electro- UV-VIS absorption spectra were recorded in a Simadzu Spectro-
chemical (EC), infrared (IR), or gas chromatography–mass photometer (model UV-1800). The photoluminescence (PL)
spectroscopy (GC–MS) methods, or field-effect transistors are spectra were recorded on a Fluoromax-4 (0406C-0809) spectro-
quite costly, and efficient molecular sensors based on AIEE fluorophotometer. The steady state photoluminescence spectra
materials could represent a real breakthrough in this area. were recorded on a Spectrofluorometer FLS920-s Edinburgh.
The quantum efficiency (QE) in solution for 1–4 has been
measured with respect to coumarin 153 (in degassed ethanol,
2. Materials, methods QE = 0.38, excitation 400–420 nm). High-resolution MS (HRMS)
and characterization experiments were carried out with a (TOF MS ES+1.38 eV) VG
Analytical (70-S) spectrometer and a Q-Tof micro mass spectro-
2.1 Materials
meter. Infrared spectra were recorded with an FTIR Shimadzu
Ir(III) chloride hydrate, triphenylphosphine, pyridine-2-amine, (IR prestige-21) spectrometer. All the reactions were performed
pyrimidine-2-amine, 5-methylpyridine-2-amine, benzaldehyde, under a nitrogen atmosphere and the progress of the reaction
triphenylamine, phosphorous oxychloride, dimethyl formamide was monitored using thin-layer chromatography (TLC) plates
and 2-ethoxyethanol were purchased from the Sigma Aldrich (pre-coated with 0.20 mm silica gel).
Chemical Company Ltd. All spectroscopic grade solvents: dichloro- Lifetime data have been acquired with time correlated single
methane (DCM), methanol (MeOH), benzene, 1,4-dioxane, ethyl photon counting (TCSPC) instruments, suitable for a ns–ps
acetate, chloroform (CHCl3), tetrahydrofuran (THF), acetonitrile time range and nano LEDs with a 375 nm (average pulse width
(ACN), dimethylformamide (DMF) and dimethylsulphoxide of 60.4 ps) and 405 nm (average pulse width of 56.9 ps)
(DMSO) were procured from the Merck Company. excitation source at room temperature. The solid-state quantum
yield of the powder samples was measured using a calibrated
2.2 Synthesis integrating sphere in a Gemini spectrophotometer (Gemini 180).
2.2.1 Syntheses of Schiff bases. All four Schiff bases were The emission and absorption spectra of the complexes were
synthesized using the well-known condensation method. In recorded after purging the sample with N2 gas.
this case, benzaldehyde (5.30 mmol) was added respectively The highly shielded 1HNMR signal in the range of 14.39 to
to stirred solutions of pyridine-2-amine/pyrimidine-2-amine/ 14.53 ppm indicates the presence of hydride (Ir–H) in the
5-methylpyridine-2-amine (5.30 mmol) in ethanol (20 ml) complexes. This finding is further supported by the stretching
followed by a catalytic amount of acetic acid and refluxed for frequency at 2128–2176 cm 1 recorded by FTIR and the value
12 hours. The reaction mixture was evaporated under vacuum and computed using density functional theory (DFT) based methods
used without further purification. The fourth Schiff base com- at B2210 cm 1 for all the complexes. The IR stretching fre-
pound was prepared by following a similar route as described quency of CQN in the Schiff base ligands appears within the
above where the reactants taken for the condensation reaction are 1579–1610 cm 1 range and the computed DFT frequencies have
4-(diphenylamino)benzaldehyde and pyridimine 2-amine. the same order of magnitude (Table S8, ESI†). A 31P NMR signal
2.2.2 Syntheses of complexes 1–4. All four complexes were is observed in the range of 4.34–6.39 ppm. From the HRMS data,
synthesized using the previous procedure reported by our the major fragmented peak appears as [M + H]+ at m/z in the
group,35,36 where to a stirred solution of IrCl3
3H2O (0.5025 mmol) range of 936.2476–1102.2661.
in 2-ethoxyethanol (6 ml), triphenylphosphine (1.507 mmol) was Complex 1. 1H NMR (400 MHz, CDCl3) d 8.61–8.27 (m, 1H),
added and the reaction mixture was refluxed at 130 1C for 4 hours. 7.84 (d, J = 7.6 Hz, 1H), 7.44 (dt, J = 10.9, 5.4 Hz, 4H), 7.12
Then, the crude reaction mass of the respective Schiff bases (dt, J = 26.6, 7.2 Hz, 6H), 6.97 (t, J = 7.2 Hz, 1H), 6.72 (t, J =
(2.0 mmol) was added to the reaction mixture, which was further 7.4 Hz, 1H), 6.46–6.26 (m, 1H), 14.47 (t, J = 16.0 Hz, 1H);
31
refluxed for 3 hours and afterwards brought to room temperature. P NMR (162 MHz, CDCl3) d 5.69; 13C NMR (101 MHz, CDCl3) d
The resulting solid mass was triturated and washed with diethyl 176.13, 158.13, 158.13, 155.44, 144.27, 134.09, 134.04, 133.99,

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130.95, 130.68, 130.40, 130.09, 129.59, 128.68, 128.57, 128.45, Complex 4 + TFA. 1H NMR (400 MHz, CDCl3) d 13.00 (s, 1H),
127.54, 127.49, 127.44, 126.11, 113.19; IR (KBr, cm 1): 2151 8.24 (d, J = 5.4 Hz, 1H), 7.90 (d, J = 8.2 Hz, 1H), 7.65 (t, J = 7.4 Hz,
(m, nIr–H) and 1580 and 1542 (m, nCQN); ESI-HRMS, calculated: 1H), 7.38 (ddd, J = 11.5, 8.5, 6.9 Hz, 2H), 7.31–7.24 (m, 15H),
([M + H]+), m/z 936.4581, found ([M + H]+): m/z 936.2476. 7.20 (t, J = 7.4 Hz, 21H), 7.05 (d, J = 7.6 Hz, 4H), 6.79–6.68
(Fig. S1, ESI†) (t, J = 12.9 Hz,1H), 6.37 (d, J = 42.1 Hz, 2H), 15.04 (t, J =
Complex 2. 1H NMR (400 MHz, CDCl3) d 8.18 (d, J = 5.5 Hz, 14.6 Hz, 1H) (Fig. S10, ESI†).
1H), 7.51 (dd, J = 19.6, 7.7 Hz, 4H), 7.37 (ddd, J = 8.2, 6.7, 3.3 Hz,
12H), 7.06 (tt, J = 8.1, 4.1 Hz, 18H), 6.89 (t, J = 7.3 Hz, 2H), 6.66 2.4 Single crystal X-ray diffraction study
(dd, J = 17.8, 9.8 Hz, 2H), 6.52–6.22 (m, 1H), 14.49 (t, J = Single crystal X-ray diffraction data for 2 were recorded on a
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16.1 Hz, 1H); 31P NMR (162 MHz, CDCl3) d 4.34; 13C NMR Rigaku XtaLAB mini single crystal X-ray diffractometer equipped
(101 MHz, CDCl3) d 171.22, 147.18, 145.22, 137.16, 134.15, with a Mercury 375/M CCD detector and graphite mono-
Open Access Article. Published on 10 July 2017. Downloaded on 6/15/2019 [Link] AM.

134.10, 134.04, 131.51, 131.24, 130.97, 129.34, 128.89, 127.37, chromated Mo-Ka radiation. The data set was collected at
127.32, 127.28, 126.21, 117.81, 117.58; IR (KBr, cm 1): 2128 100.0(1) K by using an Oxford cryosystem. The data were
(m, nIr–H), 1603 (m, nCQN); ESI-HRMS, calculated: ([M + H]+), processed using Rigaku CrystalClear suite 2.0.61 The crystal
m/z 935.2063, found ([M + H]+): m/z 935.3567 (Fig. S2, ESI†). structure was solved by using SHELXS201362 and refined using
Complex 3. 1H NMR (400 MHz, CDCl3) d 7.81 (s, 1H), 7.54 SHELXL2013, available within Olex2.63 All the hydrogen atoms
(d, J = 7.5 Hz, 2H), 7.48–7.36 (m, 12H), 7.21–7.12 (m, 7H), 7.12– have been fixed at their geometrically ideal position and have
7.04 (m, 11H), 6.98–6.88 (m, 1H), 6.73 (dd, J = 8.2, 7.4 Hz, 2H), been refined isotropically using the riding model. Geometric
1.89 (s, 3H), 14.48 (t, J = 15.8 Hz, 1H); 31P NMR (162 MHz, calculations have been carried out using PARST.64
CDCl3) d 5.69; 13C NMR (101 MHz, CDCl3) d 169.12, 146.62,
145.41, 137.79, 134.14, 134.09, 134.03, 131.45, 131.18, 130.92, 2.5 Computational details
129.22, 128.65, 127.28, 127.23, 127.18, 126.20, 117.41, 18.40. IR Electronic structure calculations were performed within the
(KBr, cm 1): 2151 (m, nIr–H), 1612 and 1567 (m, nCQN) ESI- DFT framework. Geometry optimizations of the ground state
HRMS, calculated: ([M + H]+), m/z 949.2219, found ([M + H]+): (S0) and lowest triplet state (T1) were carried out with the B3LYP
m/z 949.2698 (Fig. S3, ESI†). hybrid functional,65 the double-z quality basis set consisting of
Complex 4. 1H NMR (400 MHz, CDCl3) d 8.34 (d, J = 4.9 Hz, Hay and Wadt’s effective core potential (LANL2DZ) for the
1H), 7.62 (d, J = 8.2 Hz, 2H), 7.51–7.35 (m, 14H), 7.33–7.07 iridium atom and the standard all-electron 6-31G(d) basis set
(m, 22H), 7.01 (dd, J = 15.9, 7.7 Hz, 6H), 6.44 (dd, J = 15.3, for all other elements.66–68 Optimized geometries were identified
7.6 Hz, 3H), 14.43 (t, J = 16.2 Hz, 1H); 31P NMR (162 MHz, as true local minima with no imaginary frequencies within the
CDCl3) d 4.53; 13C NMR (101 MHz, CDCl3) d 171.39, 148.62, harmonic approximation. Vertical transition energies at the S0
147.48, 147.27, 139.47, 137.14, 134.31, 134.25, 134.20, 131.59, and T1 geometries were computed via time-dependent DFT
131.32, 131.05, 129.36, 128.96, 127.40, 127.35, 127.30, 124.20, (TDDFT) with the same energy functional and basis set. The
122.69, 121.40, 117.49, 117.12; IR (KBr, cm 1): 2176 (m, nIr–H), absorption spectra were simulated by convolution of Gaussian
1580 (m, nCQN); ESI-HRMS, calculated: ([M + H]+), m/z functions with a half-width at half maximum (HWHM) of
1102.2798, found ([M + H]+): m/z 1102.2661 (Fig. S4, ESI†). 3500 cm 1. The vibrationally resolved emission spectra from
DEA. 1H NMR (400 MHz, CDCl3) d 2.53 (q, J = 7.2 Hz, 1H), T1 were simulated within the Franck–Condon approximation as
0.98 (t, J = 7.2 Hz, 2H). 13C NMR (101 MHz, CDCl3) d 44.36, described by Barone et al.69 and a HWHM of 650 cm 1 was used
15.17 (Fig. S5, ESI†). for the Gaussian convolution. All calculations were carried out
DEA CO2 (a CIL). 1H NMR (400 MHz, CDCl3) d 3.16 (s, 1H), considering isolated molecules in a vacuum, except for the
2.69 (s, 2H), 1.10 (s, 3H), 0.98 (s, 1H). 13C NMR (101 MHz, optimization of the S0 and intra-ligand charge transfer (ILCT)
CDCl3) d 42.17, 40.63, 13.98, 12.67 (Fig. S6, ESI†). singlet state of complex 4, for which the IEF-PCM method70 was
Complex 1 + TFA. 1H NMR (400 MHz, CDCl3) d 10.02 (s, 1H), employed in order to account for equilibrium solvation. In
8.63 (d, J = 5.4 Hz, 5H), 8.26 (d, J = 5.5 Hz, 4H), 7.94 (dd, J = 8.3, addition, the CAM-B3LYP functional71 was used for the optimi-
1.4 Hz, 2H), 7.79–7.48 (m, 13H), 7.38 (td, J = 6.9, 3.4 Hz, 43H), zation of the 1ILCT state of 4 to account for the strong charge-
7.32–7.22 (m, 27H), 7.18 (t, J = 7.4 Hz, 33H), 7.07–6.90 (m, 8H), transfer nature of this transition, not properly described by the
6.75 (s, 5H) (Fig. S7, ESI†). B3LYP functional.72 Interactions between ACN molecules and
Complex 2 + TFA. 1H NMR (400 MHz, CDCl3) d 13.56 (s, 1H), Ir(III) complexes in the crystal structure were analyzed using two
8.12 (d, J = 5.5 Hz, 1H), 8.00 (d, J = 8.2 Hz, 1H), 7.76–7.66 molecular models: (i) two Ir(III) complexes and the central ACN
(m, 1H), 7.46–7.32 (m, 16H), 7.23 (t, J = 7.4 Hz, 8H), 7.19–7.12 molecule and (ii) one Ir(III) complex with two ACN molecules
(m, 10H), 6.89 (dd, J = 8.3, 7.6 Hz, 2H), 6.78 (dd, J = 9.6, 3.4 Hz, interacting via both PPh3 ligands. Interaction energies between
1H), 14.93 (t, J = 14.3 Hz, 1H) (Fig. S8, ESI†). ACN molecules and Ir(III) complexes were computed by applying
Complex 3 + TFA. 1H NMR (400 MHz, CDCl3) d 13.34 (s, 1H), the standard counterpoise correction for the basis set super-
7.84 (d, J = 8.3 Hz, 1H), 7.71 (s, 1H), 7.47 (dd, J = 8.3, 1.5 Hz, 2H), position error73 at the M06-2X/LANL2DZ,6-31G(d,p) level.74 The
7.38 (dt, J = 11.1, 5.5 Hz, 14H), 7.23 (t, J = 7.3 Hz, 7H), 7.15 origin of the observed disorder for solvent molecules in the
(t, J = 7.4 Hz, 12H), 6.89 (t, J = 7.9 Hz, 2H), 2.11(s, 3H) 14.95 crystal structure was also investigated at the M06-2X/LANL2DZ,
(t, J = 14.0 Hz, 1H) (Fig. S9, ESI†). 6-31G(d,p) level by carrying out a fixed rotation of the methyl

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group of one ACN molecule in the presence of the two neighbor-

ing interacting Ir(III) complexes with fixed geometries. Color
coordinates for compounds 1–4 were calculated from the experi-
mental emission spectra in the standard CIE (21) 1931 color
space following the conventional procedure75 (ESI†). All electro-
nic structure calculations were performed using the Gaussian09
package.76
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3. Results and discussion

3.1 Molecular and electronic structure
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All synthesized complexes have a single Ir(III) metal center in a

Fig. 1 Molecular orbital diagram of 2 at the ground state geometry
distorted octahedral coordination environment. Complexes 1–4 optimized at the B3LYP/LANL2DZ,6-31G(d) level. Participation of fragment
contain two triphenylphosphine ligands (PPh3) axially coordinated orbitals to the whole system’s MOs is indicated by the following color
with the Ir(III) atom, since our previous studies suggested that code: red for d-block orbitals of the iridium atom; light green for p orbitals
these highly mobile groups could be responsible for the observa- of the chloride ligand; dark green for p and p* type orbitals of the phenyl
rings of the phosphine ligands; blue for n, p and p*-type orbitals of the
tion of an enhanced emission in aggregated phases.20,37,77 The
Schiff base ligand and orange for s-type orbitals of the phosphorous’s lone
four coordination positions on the equatorial plane are occupied pairs. Hydrogen atoms are omitted from the picture for the sake of clarity.
by the N and C atoms of a Schiff base bidentate ligand, a chloride,
and a hydride ligand. The differences between the four synthesized
complexes are in the Schiff base ligand (Scheme 1). Concretely,
complex 1 contains a pyrimidine ring, while complexes 2 and 3 diagram for complex 2. Due to the heterogeneous ligand
have pyridine and methylpyridine moieties instead, respectively. substitution pattern, all d-type orbitals from the Ir atom exhibit
Complex 4 corresponds to the substitution of the Schiff base with a sizable mixings with ligand orbitals. In particular, Ir orbitals in
diphenylamine donor group. the t2g-like set combine with occupied p-type orbitals from the
The principal geometrical parameters describing the distorted chloride ligand, the lone pairs of the phosphorous atoms and
octahedral environment of the Ir(III) atom in complex 2 are p-type orbitals from the Schiff base ligand. The two highest
gathered in Table S2 (ESI†). Optimized bond distances and angles occupied MOs, HOMO and HOMO 1, of complex 2 are practi-
for the ground state are in very good agreement with the X-ray cally degenerate combinations of metal dxy with chlorine py and
molecular structure. A detailed discussion of the differences metal dxz with chlorine pz AOs, respectively, with the HOMO 1
between the experimental and calculated geometries can be found having an additional participation of p-type orbitals of the
in the ESI.† Schiff base ligand. The lowest unoccupied orbitals correspond
Next we analyze in detail the electronic structure of the mainly to p*-type orbitals of the Schiff base ligand. The lowest
synthesized compounds by means of their frontier occupied unoccupied MO (LUMO) has a small contribution of the Ir
and virtual molecular orbitals (MOs). In the following we refer atomic orbitals, while the LUMO+3 shows participation of
to the z-axis as the one in the P–Ir–P direction and the x-axis orbitals from two phenyl rings on the phosphine ligands.
defined by the C–Ir–Cl direction. Fig. 1 depicts the MO energy Further details regarding the MOs of 2 can be found in the ESI.†
The MO diagrams for complexes 1 and 3 are qualitatively
very similar to that of 2, except for subtle differences in the
energies of the orbitals and the degree of mixing of fragment
orbitals due to the differences in the Schiff bases. There is,
though, an important difference between 4 and the other three
complexes. Substitution of the Schiff base with an electron-
donating diphenylamine group modifies dramatically its elec-
tronic structure. The HOMO is no longer an orbital centered on
the iridium atom, but a pure p-type orbital of the donor amine
unit (Fig. 2). The remaining frontier MOs of 4 are equivalent
to those of 2.

3.2 Photophysical properties in solution and thin films

The lowest computed singlet and triplet states of complexes 1–3
correspond to excitations from the dxy and dxz type HOMOs to
the Schiff base centered LUMO. Amplitude analysis of these
excitations reveals that the corresponding excited states have
important metal-to-ligand charge transfer (MLCT), ligand-to-
Scheme 1 Synthesis of complexes 1–4. ligand charge transfer (LLCT) from the chloride to the Schiff

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Fig. 2 HOMO and LUMO of the optimized ground state of 4 at the

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B3LYP/LANL2DZ,6-31G(d) level. Hydrogen atoms have been omitted for

the sake of clarity.
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base, and ligand-centered (LC) p,p* character in the case of the

excited state involving the dxz based occupied orbital. For
simplicity, we will from now on refer to these excited states
5
as MLLCTy and MLLCTz/LC, where y and z indicate the atomic Fig. 3 UV-VIS absorption spectra (in arbitrary units) of 1–4 (10 M)
p orbital of the chlorine atom involved in the occupied MO of recorded in degassed DCM at room temperature.
the transition. The lowest excited singlet state for complexes
1–3 is MLLCTy, while the lowest triplet corresponds to MLLCTz/LC.
In contrast, the lowest computed singlet and triplet states of All complexes present structured emission profiles with a separa-
complex 4 correspond to HOMO to LUMO transitions with ILCT tion between the peaks on the order of 1300–1400 cm 1, which
character due to the donor nature of the diphenylamine sub- we assign to vibronic progressions.21,78,79 The position and
stitution in the Schiff base. The computed vertical excitation relative intensity of the vibronic peaks in the thin film emission
energies to these states are gathered in Table 1. spectra are very close to their counterparts in solution. This
The UV-VIS absorption spectra in DCM solution for 1–4 are matching is also reflected when comparing the emission colors
shown in Fig. 3. The moderately intense band at 300–450 nm in thin film with the emission colors in DCM solution shown in
is assigned by our calculations to the 1MLLCTz/LC state computed the chromaticity diagram (Fig. 5 and Table S4, ESI†), for which
at B370 nm for all complexes. The absorption profiles of complexes the same green to yellow transition is observed.
1–3 are very similar to each other, as predicted by the correspon- Our calculations predict the 3MLLCTz/LC state as the one
dence of their MO diagrams (Fig. 1). The absorption spectrum of responsible for the phosphorescence emission of complexes
complex 4 exhibits a rather intense band centered at B400 nm not 1–3. For all three complexes there is a nice agreement between the
present for the other three complexes, which is a signature of the experimental emission spectra and the simulated vibrationally
ILCT transition in the Schiff base ligand. The vertical transition to resolved phosphorescence profiles (Fig. 6, Fig. S32 and S33, ESI†).
1
ILCT in 4 is computed at 416 nm, in very good agreement with the For complexes 1–3, the main vibrational mode responsible
experimental absorption maximum (404 nm). The simulated spectra for the structured emission is related to the stretching of the
of all complexes (ESI†) reproduce reasonably well the band positions CQN bond in the Schiff base, with a computed frequency of
and relative intensities of the experimental absorption spectra. B1470–1450 cm 1 (Fig. S34, ESI†). The distortion associated with
We have explored the solvent polarity dependence of the this mode is in fact the main geometrical modification along the
absorption spectra of the studied complexes. While the absorp- molecular relaxation on the T1 state potential energy surface from
tion spectra of 1–3 show no dependence on solvent polarity, the the Franck–Condon region. Although this vibrational progression
absorption spectrum of complex 4 shows a weak dependence is the main contribution defining the overall shape of the emission
with the solvent dielectric constant due to the strong absorp- spectra, there are other less intense normal modes also contribut-
tion of the 1ILCT state and its CT character (Fig. S13, ESI†). ing to the emission profiles (Tables S5–S8, ESI†).
The normalized emission spectra of the synthesized com- The emission spectrum of 4 in solution exhibits two clearly
plexes in DCM solution and in thin film are shown in Fig. 4. distinct bands (Fig. 7): (i) a solvatochromic band at 400–525 nm
and (ii) a structured emission band in the 525–700 nm region,
very similar to the emission band in 1–3, that is practically
Table 1 Vertical excitation energies (in nm) and oscillator strengths independent of the solvent’s polarity (Fig. S14, ESI†). Due to
Z0.01 (in parenthesis) for the lowest excited states of 1–4. All values
this dual emissive behavior, the emission color of 4 may easily
computed at the B3LYP/LANL2DZ,6-31G(d) level
be tuned by varying the solvent’s polarity. In particular, in low
State 1 2 3 4 polarity solvents (benzene, 1,4-dioxane), the emission color
3
MLLCTz/LC 456 472 479 420 of 4 is blue with an emission band maximum at 461 nm,
3
MLLCTy 406 397 395 395 whereas in more polar solvents (ethyl acetate, CHCl3, DCM
3
ILCT — — — 528 and THF) the emission gradually shifts to longer wavelengths.
1
MLLCTz/LC 370 (0.02) 368 (0.04) 368 (0.07) 365 (0.01)
1
MLLCTy 397 389 387 387 In strongly polar solvents (DMSO) complex 4 shows yellow
1
ILCT — — — 416 (0.58) emission (Fig. 7).

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Fig. 4 Normalized emission spectra of 1–4 in degassed DCM at room temperature (left) and thin film (right).

Fig. 5 Chromaticity diagram for the emission of 1–4 in DCM (left) and their respective thin film emission color under 365 nm UV lamp (right).

The similarities of the emission of 4 in the 525–700 nm agreement with the shift observed in the experimental spectra
region with the emission spectra of complexes 1–3 allow us to (0.12 eV). As the polarity of the solvent increases, the LUMO is
assign this band to the phosphorescence emission from the more stabilized than the HOMO (Table S12, ESI†), leading to the
3
MLLCTz/LC state. On the other hand, our calculations indicate observed red-shift in the emission energy. Further calculations
that the state responsible for the solvatochromic band below ruling out the possible formation of a twisted intramolecular
500 nm corresponds to the singlet state with ILCT character. charge transfer state (TICT) may be found in the ESI.†
This assignment is also supported by time-resolved photo- The observed red-shifted emission of the fluorescent ILCT
luminescence measurements by monitoring the emission maxima band in highly polar solvents of 4 is also accompanied by a
at 450 nm and 530 nm in different solvents (benzene, DCM, THF decrease in its PL intensity. This is clearly seen in Fig. 8, where
and DMSO). The lifetime data for the high-energy band is obtained the emission spectra of 4 recorded with different fractions of
within the 0.9–1.4 ns range, consistent with fluorescence emission benzene ( fB) in THF are shown. The gradual addition of
(Fig. S15–S18 and Table S1, ESI†). On the other hand, the lifetime benzene to the THF solution results in a blue shifted emission
measurements of the band at 530 nm are in the microsecond with increasing PL intensity. The spectral data reveal that the
range (from 1.4 to 1.7 ms), consistent with phosphorescence intensity of the short wavelength band gradually increases with
emission. The 1ILCT state of 4 was optimized in strongly polar increasing benzene fractions.
and non-polar solvents, i.e. DMSO and benzene, for which the Frozen samples of 4 in benzene and 1,4-dioxane at 80 1C
experimental emission maxima were measured at 480 and 459 nm, showed yellow emission under excitation at 365 nm (Fig. S19,
respectively. The calculated relative shift in the vertical emission ESI†), while at room temperature a blue emission was observed.
energies of 4 in benzene and DMSO is 0.16 eV, in very good Since the yellow emission of 4 has been attributed to the

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insoluble in water, thus we explored the effects of aggregation

on their PL properties in THF–water with a wide range of
mixing ratios. The formation of aggregates when water is
present was confirmed using a particle size analyzer, indicating
the formation of nano-aggregates with diameters in the range
of 124–674 nm (Fig. S11, ESI†). Solutions of 1–3 in pure THF
emit weakly, while their emission gradually increases with the
water fraction in THF–water mixtures. For mixtures with a high
content of water (fw = 90%), the PL intensity of complexes 1, 2
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and 3 is 45, 18, and 6 times stronger than that in pure THF
solution (Fig. S21, ESI†), respectively.
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The AIEE property of 4 was also investigated in different

solvents, namely THF, ACN and DMSO with gradual addition of
water. The dilute solution of THF shows a faint green photo-
Fig. 6 Simulated (solid line) and experimental (dashed line) phosphores- emission that intensifies and red shifts (from 535 nm to
cence emission spectra of complex 2. Vertical sticks indicate the relative
578 nm) at fw = 10%. The addition of more water, ( fw = 20%),
strength of vibronic transitions contributing to the simulated spectrum.
Both spectra have been normalized and the calculated spectrum has been leads again to a red shifted emission maximum (from 578 nm
blue shifted by 0.12 eV to superimpose the most intense peaks. The 204 to 610 nm) and to an increase of the emission intensity. We
normal mode of vibration resulting in the vibrational structure corresponds attribute this spectral change (red shifted emission) to the
to the CQN stretching mode of the imine. stabilization of the charge transfer state with increasing solvent
polarity.80 A further increase of the water fraction up to 70%
does not alter the emission maximum and its intensity. At
3
MLLCTz/LC state, this suggests that molecular relaxation of fw = 80% however, a sudden blue shifted structured emission
the 1ILCT state from the Franck–Condon geometry is slowed (516 nm and 557 nm) appears along with a slight increase in
down in the frozen samples, allowing the population of the the PL intensity. In contrast, the emission red shifts again
3
MLLCTz/LC state via intersystem crossing. (from 535 nm and 574 nm) at fw = 90%, but the structured
Finally, the excitation and emission spectra recorded in profile remains and the PL intensity is 22 times higher than
different solvents are in agreement with a dual emission from that in pure THF (Fig. 9). In this case, the observed emission
two different states, i.e. 1ILCT and 3MLLCTz/LC (Fig. S20, ESI†). enhancement at higher water content can also be safely attrib-
uted to aggregate formation (Fig. S11, ESI†). In addition, we
3.3 Aggregation-induced enhanced emission argue that closely spaced aggregates could be responsible for
All four synthesized complexes exhibit weak emission in com- creating a less polar environment, resulting in a blue shifted
mon organic solvents such as DCM, THF, MeOH, CHCl3, ACN, emission.81,82
or DMSO, but they are highly emissive in the solid state. Such The emission behavior of 4 was also studied using mixtures
strong solid-state emission encouraged us to study the AIEE of with different ACN–water fractions (Fig. S22, ESI†). The emis-
these complexes. Complexes 1–3 are highly soluble in THF but sion intensity of 4 doubles at fw = 30% in comparison to pure

Fig. 7 (a) Emission spectra of 4 in different solvents. (b) Photographs showing the emission colors of 4 under UV light in different solvents (from left to
right): benzene, 1,4-dioxane, ethyl acetate, CHCl3, DCM, THF and DMSO. Concentration of 4 in all cases: 1  10 5 M. The spectra have been normalized
to the peak at B535 nm.

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Fig. 8 (a) Emission spectra of 4 in THF with different benzene fractions (0–90%). (b) Plots of maximum emission intensity and wavelength of 4 versus
benzene fraction (fB) in the THF/Benzene mixture. Solution concentration: 1  10 5 mM. (c) Photographs of 4 in THF/benzene mixtures with different
fractions of benzene (fB) taken under 365 nm UV illumination.

Fig. 9 (a) Emission spectra of 4 in THF/water mixtures (0–90%). (b) Plot of maximum emission intensity and wavelength of 4 versus water fraction.
Concentration of 4: 1  10 5 M. (c) Photographs of 4 in THF/water mixtures taken under UV illumination.

ACN solution, while the emission maximum remains at The formation of nanoaggregates in the AIEE experiments of
510 nm. At fw = 50% the PL intensity increases by 5 times with complex 4 was confirmed by the leveled-off tails81 in the visible
respect to pure ACN solution and the emission maximum slightly region of the recorded UV-VIS spectra in different water
red-shifts to 523 nm. Further addition of water ( fw = 70%) fractions with DMSO, as well as with ACN (Fig. S23, ESI†).
increases the PL intensity by 5 times in comparison to pure The AIEE of these complexes was further studied by measur-
ACN solution, but now the emission band is no longer broad, ing the absolute emission quantum yields (QY) for solid
displaying two distinct peaks at 517 nm and 552 nm, respectively. samples, and comparing these data with those obtained in DCM
The structured band remains at fw = 90% with a significant red solution. The QY of these complexes in solution is o0.1%, while
shift to 538 and 580 nm, however, the PL intensity weakens the absolute QY in the solid state is 3–9% that is, about two orders
dramatically to only thrice that of the pure ACN solution. of magnitude higher.
The emission spectra of 4 in DMSO–water mixtures do not In order to explore the possibility of whether weak inter-
show any changes in the emission maximum, since there is molecular interactions could be responsible for the restriction
already a highly polar environment in the pure organic solvent, of intramolecular motions83,84 in the solid state and give rise to
but the PL intensity increases by 32 times as compared to the an enhancement of the PL intensity upon aggregation, the
pure DMSO solution of the complex (Fig. 10). crystal packing of 2 was analyzed in detail considering that it

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5
Fig. 10 (a) Emission spectra and (b) plot of maximum emission intensity of 4 in DMSO/water mixtures (0–90%). Concentration of 4: 1  10 M.
(c) Photographs of 4 in DMSO/water mixtures taken under UV illumination (excitation at 365 nm).

might represent an acceptable structural model for the aggre-

gates formed in the mixtures of water with organic solvents.
The crystal structure of 2 has a unit cell with four equivalent
Ir(III) complexes together with four cocrystallized ACN mole-
cules exhibiting disorder in the position of their hydrogen
atoms. Iridium complexes arrange in chains along the b-axis,
with each chain being surrounded by six other chains in an
approximate elongated hexagonal fashion as shown in Fig. 11.
The molecules of the reference chain (highlighted in red) lie in
the same ac-plane as the chains highlighted in grey. On the
other hand, the chains shown in blue are displaced by half a
unit cell along the b-axis with respect to the reference chain.
Inspection of interatomic distances between molecules in the
reference and grey chains indicates the absence of potentially
important non-covalent interactions between them. The reference
and blue chains, however, exhibit short interchain C–H


Cl
distances (2.802 Å) between the chloride ligand and a hydrogen
atom from an adjacent PPh3 ligand, indicative of non-negligible
interchain interactions that represent a possible source of restric-
tion of molecular motions in the solid state (Fig. S37, ESI†).
Nevertheless, the most significant interactions are found along
the chains themselves, where crystallized ACN solvent molecules
alternate with iridium complexes, as shown in Fig. 12. An analysis Fig. 11 Crystal packing of 2 with a reference chain highlighted in red.
of intermolecular distances hints to the presence of strong C–H


Cl interactions (2.802 Å) between the chains are shown in green.
Atom color code: nitrogen in blue, phosphorous in orange, chlorine in
C–H


p interactions between each ACN molecule and two phenyl
green, carbon in black and hydrogen in white. Hydrogen atoms
rings from PPh3 ligands of adjacent complexes. The computed not involved in intermolecular interactions are omitted for the sake of
interaction energy between one complex with the two neighboring clarity.
ACN molecules was 9.1 kcal mol 1, confirming the presence of
these C–H


p interactions.
Further calculations were carried out to investigate the molecule considering a fixed geometry was carried out in the
origin of the observed disorder for the hydrogen atoms of presence of the two neighboring complexes (see Computational
the ACN molecules in the crystal structure. Calculation of the details). Two minima were obtained corresponding to the two
energy cost for a rotation of the methyl group of the solvent hydrogen configurations found in the resolution of the crystal

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important role in the solid state photophysics of iridium

complexes.20

3.4 Reversible protonation–deprotonation

We also performed photophysical studies of complexes 1–4 in
the presence of TFA/Et3N. Interestingly, addition of TFA triggers
a considerable bathochromic shift in the thin film emission
spectra of 1 and 4. The exposure of a thin film of 1 to TFA
results in a broad emission band with a maximum at 539 nm
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responsible for a yellow color, which is highly reversible to its

original green emission with maxima at 484 nm and 517 nm
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after exposure to Et3N (Fig. 13). The yellow emitting thin film of
4 becomes red emissive with an emission maximum at 617 nm
upon exposure to TFA. Likewise, subsequent Et3N addition
leads back to its original yellow emission. The thin films of
complexes 2 and 3 also present reversible modification of the
emission spectra under TFA/Et3N, although the emission color
change is less pronounced (Fig. S24, ESI†).
Fig. 12 C–H


p interactions between ACN molecules and Ir(III) com- The reversibility of such protonation/deprotonation processes is
plexes along the crystal chains and inter-chain C–H


Cl interactions with confirmed by the 1H NMR spectra of the protonated complexes
the chains highlighted in blue in Fig. 11. ACN molecules present dynamic
(1–4) recorded in CDCl3 solution. 1H NMR of complex 1 after
disorder.
exposure of the film to TFA shows a downfield signal at
d = 9.01 ppm, not present in the absence of TFA. Similarly 2,
structure. The computed energy barrier (0.3 kcal mol 1) for the 3 and 4 display an even more downfield signal at d = 13.56,
interconversion of the two conformations lies below the 13.33, and 12.99 ppm, respectively. These 1H NMR spectra
thermal energy kT at the temperature of crystal determination indicate the transformation of these complexes into a proto-
(0.4 kcal mol 1), suggesting that the origin of the observed nated form, where the downfield 1H signals may be attributed
disorder in the crystal structure is dynamic rather than static. to the protonation of the nitrogen atom in the imine ligand unit
These calculations show that in the crystal we should expect the (Fig. S12, ESI†). Electronic structure calculations also suggest
methyl groups to rotate quite freely, establishing thus C–H


p that the energetically most favorable protonation occurs on the
interactions that restrict the motion of the PPh3 ligands and iminic nitrogen for all complexes (Table S9, ESI†). Computation
block non-radiative decay channels in the solid state with an of the protonated cationic form of complex 2 (labeled as 2H)
increase of the emission intensity as a result. It has been indicates that the most important geometrical difference with
recently shown that these types of interactions might play an respect to the neutral complex is the larger torsion angle of the

Fig. 13 Thin film reversal of emission color upon TFA/Et3N exposure and emission spectra of complexes 1 (a and b) and 4 (c and d). The thin-film
photographs and PL spectra were taken under an excitation wavelength of 365 nm and 400 nm, respectively.

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Fig. 14 (a) Emission spectra of 4 in DEA with different fractions of CIL (0–90%). (b) Maximum emission intensity with respect to CIL. (c) Photographs of 4
in DEA/CIL mixtures taken under UV illumination.

phenyl ring of the Schiff base ligand due to steric hindrance factors responsible for the broad emission band with no vibra-
between one of its hydrogen atoms and the protonating hydro- tional structure observed upon exposure of the complexes to
gen (Fig. S38, ESI†). In the unprotonated complex, the Schiff TFA: (i) the absence of LC character in the emitting triplet state,
base ligand is completely planar, while in the 2H form the (ii) the loss of ligand planarity and (iii) the increase of molecular
phenyl ring experiences a torsion of 221 with respect to the flexibility.
complex’s equatorial plane. Other structural differences of The dependence of the emission profiles for these complexes
the coordination sphere of complex 2 upon protonation may with pH suggests that these materials are potential candidates
be found in the ESI† (Table S10). for H+ detection. Additional spectra of 1–4 in solution with the
Protonation of the molecular species disrupts their electronic presence of TFA may be found in the ESI† (Fig. S25 and S26).
properties, resulting in changes in their photophysical behavior.
Concretely, there is a reduction of the HOMO–LUMO gap upon 3.5 CO2 detection
protonation. Moreover, in the protonated form the electron The solubility of 4 was screened with different amines, e.g.
density on the Schiff base ligand is strongly stabilized. As a pyridine, 1,8-diazabi-cyclo-[5,4,0]-undec-7-ene (DBU), piperidine
result, the highest occupied orbitals with dxz and dyz participa- and diethyl amine (DEA). Complex 4 was found to be completely
tion do not show contributions from the conjugated systems of soluble in DEA. The reaction between DEA and CO2 yields a
the bidentate ligand (Fig. S39, ESI†), and the computed excita- viscous carbamate ionic liquid (CIL). In this case, the CIL was
tion energies to the 3MLLCTy and 3MLLCTz states are very close synthesized by a simple reaction condition where the DEA
to each other (Table S11, ESI†). These results point towards three solution was purged by a large excess of CO2 gas for 10 minutes.

Fig. 15 (a) PL spectra of 4 in DPA with different volumes of CO2 displaying a gradual enhancement of the PL intensity. (b) The PL intensity increased in a
linear fashion (R2 = 0.9970) with gradual addition of CO2.

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The synthesized CIL was characterized by 1H NMR and 13C NMR films upon TFA exposure. An easy method for CO2 detection was
spectroscopy and the results matched satisfactorily with earlier also developed with 4 using a phosphorescence technique
reports54 (Fig. S6, ESI†). controlled by the viscosity of the medium. All the properties
The weak emission of complex 4 in DEA solution becomes studied in this work point towards the potential application of the
gradually more intense after purging of CO2 bubbles. In fact, newly synthesized complexes as multi-responsive luminescent
there is a linear relationship between the amount of CIL materials.
gradually added into the solution (fCIL) and the emission
intensity of the sample. At fCIL = 90%, the PL intensity is
2.4 times stronger as compared to the intensity of the DEA Acknowledgements
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

solution (Fig. 14). This emission enhancement may be attributed

to the increase in the viscosity of the medium that leads to a This work was supported by the Basque Govt. (project IT588-13)
Open Access Article. Published on 10 July 2017. Downloaded on 6/15/2019 [Link] AM.

restriction of the motion of the phenyl rings in the PPh3 ligands and the Spanish Govt. (MINECO/FEDER projects CTQ2015-
possibly responsible for non-radiative decay. The increase of the 64579-C3-3-P and CTQ2016-80955). We are thankful to DST,
PL intensity of complex 4 with the viscosity of the environment Govt. of India, under a project (no. SB/S1/IC-13/2014) and CSIR,
has been confirmed by comparing the emission spectra in Govt. of India, (no. 01/2551/12/EMR-II) for financial assistance.
PEG–THF mixtures (Fig. S27, ESI†). To further analyze the The UGC-SAP and DST-FIST, Govt. of India, are acknowledged
response of 4 in DEA solutions to CO2, additional experiments for the instrumental support to the Department of Chemistry,
were carried out in which different fractions of CO2 were purged BITS Pilani. We thank Dr Neetu Singh, advanced instrumentation
through a solution of 4 in DEA at a fixed rate and time. The research facility, JNU, New Delhi (India), for providing technical
emission of 4 was enhanced by gradual addition of CO2 in the help on time resolved fluorescence spectroscopy. IISER Mohali is
system and resulted in a linear plot for the whole concentration acknowledged for providing the X-ray diffraction and NMR facilities.
range. These results indicate the potential use of DEA diluted D.C. thanks IKERBASQUE, Basque Foundation for Science for
complex 4 as a quantitative detector of CO2 (Fig. 15). Although financial support. C.C. is indebted to the Spanish ‘‘Ministerio de
the addition of CO2 facilitates the removal of O2 from the sample Economı́a y Competitividad’’ for a predoctoral FPI grant.
which might result in a larger emission intensity, it cannot
account for the large PL intensity increase observed.
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