New iridium complexes with two pre-organized urea groups and thiourea groups as phosphorescent chemosensors for H2PO4 - and chiral carboxylates

Article abstract of DOI:10.1016/j.dyepig.2013.09.018

As a versatile platform for phosphorescent chemosensors, bis(benzylic amine) derivative 6 was synthesized. Two urea groups could be readily introduced for phosphorescent chemosensor 1. A preorganized binding pocket could induce a selective phosphorescence

Full text of DOI:10.1016/j.dyepig.2013.09.018

Accepted Manuscript
New Iridium Complexes with Two Pre-organized Urea Groups and Thiourea Groups
as Phosphorescent Chemosensors for H PO - and Chiral Carboxylates
2
4
Yinan Li, Liu Yifan, Dayoung Nam, Sungnam Park, Juyoung Yoon, Myung Ho Hyun
PII:
S0143-7208(13)00343-4
10.1016/j.dyepig.2013.09.018
DYPI 4092
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 9 August 2013
Revised Date: 6 September 2013
Accepted Date: 11 September 2013
Please cite this article as: Li Y, Yifan L, Nam D, Park S, Yoon J, Hyun MH, New Iridium Complexes with
Two Pre-organized Urea Groups and Thiourea Groups as Phosphorescent Chemosensors for H PO -
2
4
and Chiral Carboxylates, Dyes and Pigments (2013), doi: 10.1016/j.dyepig.2013.09.018.
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ACCEPTED MANUSCRIPT
Highlights
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As a versitle platform for phosphorescent chemosensors, bis(benzylic amine)
derivative 6 was synthesized.
A phosphorescent chemosensor 1 displayed a selective phosphorescence
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enhancement with H PO .
2
A new iridium complex 2 is reported as a first chiral phosphorescent chemosensor
for amino acids.

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New Iridium Complexes with Two Pre-organized Urea Groups
and Thiourea Groups as Phosphorescent Chemosensors for
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H PO and Chiral Carboxylates
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a†
b†
c
c
b
Yinan Li, Liu Yifan, Dayoung Nam, Sungnam Park, Juyoung Yoon * and
a
Myung Ho Hyun *
a
Department of Chemistry and Chemistry Institute for Functional Materials, Pusan
National University, Busan 690-735, Korea
b
Department of Chemistry and Nano Science, Ewha Womans University, Global Top5
Research Program, Seoul 120-750, Korea
c
Department of Chemistry, Korea University, Seoul 136-701, Korea
jyoon@ewha.ac.kr; mhhyun@pusan.ac.kr
†
equally contributed to this work
Abstract: As a versatile platform for phosphorescent chemosensors, bis(benzylic
amine) derivative 6 was synthesized. Two urea groups could be readily introduced for
phosphorescent chemosensor 1. A preorganized binding pocket could induce a
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selective phosphorescence enhancement with H PO . A new iridium complex 2
2
4
bearing two thiourea groups as well as glucopyranosyl chiral barriers is reported as a
first chiral phosphorescent chemosensor for amino acids.

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Keywords: phosphorescence chemosensor, anion recognition, dihydrogen phosphate
sensing, chiral recognition, iridium complex
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1. Introduction
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Numerous efforts have been devoted to the development of methods for the
recognition and detection of anions due to their important roles in many chemical and
biological processes [1]. Phosphorescent chemosensors have several unique
advantages, such as evident Stockes shifts, relatively long lifetimes, etc.. Because of
these unique properties, their emission spectra can be utilized to readily discriminate
from the background fluorescence normally present in biological and clinical sample
[
2].
Among the various types of phosphors, cyclometalated iridium (III) complexes
have been known to show high phosphorescence efficiency and relatively long
lifetimes and, thus, they have been utilized as efficient phosphorescent dopants in
organic light emitting diodes (OLEDs) [3]. These highly phosphorescent iridium (III)
complexes have also been utilized as phosphorescent chemosensors for anions [4],
cysteine/homocystein [5], molecular oxygens [6], cations [7], etc [8].
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Even though fluorescent chemosensors for H PO have been extensively studied
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[
9], there has been only one report that evaluated their use as phosphorescent
chemosensors.[10]
Similarily, chiral recognitions using fluorescence changes have been actively
studied [11], while there has not been an example for chiral phosphorescent

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chemosensors. In this paper, we report the first example of H PO selective
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phosphorescence chemosensor based on the iridium (III) complex. Unlike previous
anion selective phosphorescence chemosensors, probe 1 displayed phosphorescence
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enhancement in the presence of H PO . In addition, first example of chiral
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phosphorescence chemosensor and its chiral recognition towards amino acids are
reported.
In this work, we prepared bis(benzylic amine) derivative 6 as a versatile flatform.
As a proof of concept, two new phosphorescence chemosensors 1 and 2, which
contained a preorganized binding pocket, were synthesized from 6 and their unique
binding properties were studied. We believe this bis(benzylic amine) derivative 6 can
be utilized as a valuable platform for the development of new phosphorescent
chemosensors in the future.
2
2
. Experimental
.1 Materials and equipments
General methods unless otherwise noted, materials were obtained from commercial
suppliers and were used without further purification. Flash chromatography was carried
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out on silica gel (230-400 mesh). H NMR and C NMR spectra were recorded using
3
00 MHz and 75 MHz Chemical shifts were expressed in ppm and coupling constants
(J) in Hz. UV-vis absorption spectra were measured with an EVOLUTION 201
UV-visible spectrophotometer. Phosphorescence spectra were recorded on Shimadzu
RF-5301 pc spectrofluorometer.

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2
.2 Synthesis
,4’-Bis (bromomethyl)-2,2`-bipyridine 3
The bipyridine (0.90 g, 4.2 mmol) was dissolved in a mixture of 48% HBr (20 mL)
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and concentrated sulfuric acid (6.7 mL). The resulting solution was refluxed for 6 h
and then allowed to cool to room temperature, and 40 mL of water was added. The pH
was adjusted to neutral with NaOH solution and the resulting precipitate filtered,
washed with water (pH = 7), and air-dried. The product was dissolved in chloroform
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(40 mL) and filtered. The solution was dried over magnesium sulfate and evaporated
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to get a white powder. Yield: 1.2 g (85%). H-NMR (300 MHz, CDCl ) δ (ppm) 4.50
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(s, 4H), 7.38 (d, 2H), 8.45 (s, 2H), 8.68 (d, 2H).
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,4`-Phthalimidylmethyl-2,2`-bipyridine 4
A mixture of 4,4’-Bis (bromomethyl)-2,2’-bipyridine (0.26 mg, 0.7 mmol) and
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potassium phthalimide (1.4 g, 7.6 mmol) in DMF (38 mL) was heated at 50 C under
nitrogen atmosphere. After 5 h, water (60 mL) was added to the mixture, and the
organic layer was extracted with CHCl (70 mL  3). The organic layer was dried
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over anhydrous Na SO , and evaporated under reduced pressure. The residue was
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washed with methanol, and dried under reduced pressure to give colorless solid.
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Yield: 180 mg (50 %). H-NMR (300 MHz, CDCl ) δ (ppm) 8.61 (d, 2H), 8.37 (s, 2H),
3
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.87 (m, 2H), 7.74 (m, 2H), 7.28 (d, 2H), 4.93 (s, 4H).
Ir(ppy)2(dphmbpy) 5
A mixture of 4,4’-phthalimidylmethyl-2,2’-bipyridine (0.5 g, 0.47 mmol) and
[
(ppy) IrCl] (0.46 g, 0.98 mmol) in a 1:1 (v/v) dichloromethane and methanol
2 2

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solution was refluxed for 6 h. The solvents were evaporated on rotary evaporation.
The residue was dissolved in dichloromethane. The organic solution was washed with
brine and then dried over Na SO .The solvent was removed by rotary evaporator. The
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light yellow residue was purified by chromatography over silica gel
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(
dichloromethane). Yield: 290 mg (64 %). mp: 231-233 C. H-NMR (300 MHz,
CDCl ) δ (ppm) 9.89 (s, 2H), 7.87-7.80 (m, 6H), 7.78-7.71 (m, 8H), 7.60 (d, J = 7.69,
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H), 7.48 (d, J = 5.76, 2H), 7.18 (d, J = 5.76, 2H), 7.07 (t, J = 6.59, 2H), 6.97 (t, J
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=7.41, 2H), 6.85 (t, J = 7.41, 2H), 6.22 (d, J = 7.69, 2H), 5.34 (s, 4H); C NMR (75
MHz, CDCl )  (ppm) 167.92, 156.11, 150.35, 148.85, 143.65, 138.39, 134.70,
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31.96, 131.83，130.94，125.97, 125.66, 124.93, 123.92, 123.70, 122.83, 119.83,
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0.66; HR FAB-MS m/z [M ] calcd. For C H IrN O 975.2275 Found: 975.2271; IR
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(KBr pellet) cm 3408.43, 3043.37, 1715.50, 1607.29, 1393.19, 950.71, 725.18.
Ir(ppy)2(dambpy) 6
A mixture of 5 (70 mg, 0.1 mmol) and hydrazine monohydrate (140 μL, 2.9 mmol)
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in EtOH (5.3 mL) was heated at 100 C for 12 h. Saturated aqueous NaCl solution (18
mL) was added to the mixture. The mixture was adjusted to pH 12 with 50 % NaOH
solution. The organic layer was extracted with CHCl
anhydrous Na SO , and evaporated to give orange solid. Yield: 180 mg (50 %). mp >
(50 mL  3), dried over
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00 C. H-NMR (300 MHz, CDCl ) δ (ppm) 9.91 (s, 2H), 7.91-7.88 (d, J = 7.96,
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2H), 7.76-7.66 (m, 6H), 7.50 (s, 2H), 7.29 (s, 2H), 7.05-6.90 (m, 8H), 6.30 (d, J =
+
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.42, 2H), 4.17 (s, 4H), 2.47 (s, 4H); HR FAB-MS m/z [M ] calcd. For C H IrN
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15.2161 Found: 715.2163; IR (KBr pellet) cm 3408.68, 1683.71, 1507.16, 1477.29,
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418.84, 760.26.
Ir(ppy)2(dburebpy) 1
A mixture of 6 (70 mg, 0.08 mmol) and butyl isocyanate (140 μL) in
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dichloromethane (5.3 mL) was stirring at room temperature for 2 h. The solvents were
evaporated on rotary evaporation. The residue was dissolved in dichloromethane. The
organic solution was washed with brine and then dried over Na SO then removed by
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rotary evaporator. The light yellow residue was purified by chromatography over
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silica gel (dichloromethane). Yield: 180 mg (50 %). mp 224 – 225 C. H-NMR (300
MHz, CDCl ) δ (ppm) 9.33 (s, 2H), 7.90 (d, J = 7.97, 2H), 7.78-7.60 (m, 6H), 7.45 (d,
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J = 6.04, 2H), 7.22 (m, 2H), 7.05-6.97 (m, 6H), 6.93-6.87 (t, J = 6.73, 2H), 6.38 (d,
2H), 6.29 (d, J = 7.99, 2H), 4.62 (d, J = 6.04, 2H), 3.60-3.14 (m, 4H), 1.52-1.47 (m,
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H), 1.38-1.30 (m, 4H), 0.89-0.84 (t, J = 7.14, 6H); C NMR (75 MHz, CDCl ) δ
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(
ppm) 168.18, 159.06, 156.73, 155.27, 150.56, 149.29, 148.67, 143.67, 138.12,
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20.35, 14.06; HR FAB-MS m/z [M ] calcd. For C H IrN O 913.3529. Found:
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13.3527; IR (KBr pellet) cm 3408.50, 2926.48, 1669.53, 1559.23, 1268.68, 761.07.
GITC appended Iridium (III) complex 2
A solution of GITC (0.22 g, 0.56mmol) was added dropwise to a stirred methylene
chloride solution (20 mL) of compound 6 (0.2 g, 0.28 mmol). The mixture was stirred
for 2 h under nitrogen gas at room temperature. Purification by flash chromatography
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methylene chloride/ methanol = 20:1) offered 0.27 g orange solid compound 2.

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Yield: 65 % mp 226-227 C;
15.3 H NMR (300 MHz, CDCl ) δ 9.31 (s, 1H),
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.09 (d, J = 8.24, 2H), 7.71-7.85 (m, 8H), 7.50-7.52 (m, 2H), 7.00-7.05 (t, J = 7.41,
H), 6.88-6.94 (t, J = 7.41, 2H), 6.82-6.77 (t, J = 7.41, 2H), 6.25 (d, J = 8.24, 2H),
5.83-5.87 (m, 2H), 4.90-5.26 (m, 7H), 4.10-4.16 (m, 2H), 3.92-3.98 (m, 4H), 3.85 (bs,
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H), 1.86-1.93 (m, 24H), 1.72 (m, 6H). C NMR (75 MHz, CDCl ) δ 185.39, 171.08,
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70.51, 170.11, 169.68, 156.63, 152.00, 150.22, 149.66, 148.83, 143.69, 138.29,
31.86, 131.08, 127.37, 125.02, 123.45, 122.91, 119.83, 74.00, 73.37, 70.73, 68.51,
62.25, 47.07, 21.00, 20.84. HR FAB-MS m/z [M+] calcd. For C H IrN O S
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493.3722 Found:1493.3725; IR (KBr pellet) cm 3356, 3408, 1751, 1541, 1226,
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3. Results and discussion
3
.1 Synthesis
For the synthesis of probe 1 and 2, 4,4`-phthalimidyl methyl-2,2`-bipyridine (4) was
prepared by modifying the reported procedures [12]. Treatment of [(ppy) IrCl] with
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4,4`-phthalimidylmethyl-2,2`-bipyridine (4) produced the iridium (III) complex 5
containing bipyridine as the ancillary ligand appended with phthalimidylmethyl
groups with a yield of 64 % after column chromatography purification using
dichloromethane (Scheme 1). Phthalimidylmethyl iridium (III) complex 5 was then
reacted with hydrazine monohydrate to form the versatile intermediate, iridium (III)
complex (6) bearing dimethylamine groups. Finally, probe 1 and 2 were synthesized
by
treatment
of
compound
6
with
n-butyl
isocyanate
or

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,3,4,6-O-acetyl-β-D-glucopyranosyl isothiocyanate (GITC), respectively, at room
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temperature in dichloromethane. The detailed synthetic procedures are explained in
1
the Experimental Section and the new compounds were fully characterized by H
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NMR, C NMR and high resolution mass spectroscopy.
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Insert Scheme 1
3.2 Spectral studies of iridium (III) complex 1
The assay methods for UV-vis spectra and phosphorescence spectra: Firstly, Ir(II)
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complexes were dissolved in distilled CH Cl to make 1.0×10 M solution. Then the
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solution was diluted to quartz cell filled with 3 mL acetonitrile using microsyringe to
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1.0×10 M test solution. And because of the emission sensitivity to oxygen, all
samples in phosphorescence experiments were deaerated with argon for ca. 8 min
before measurement and the gas flow is kept during the measurement.
The UV-vis spectra and phosphorescence spectra of iridium (III) complex 1 in
acetonitrile are shown in Fig. S1. In the UV-vis spectra, due to the ligand-centered LC
1
(π-π*) and spin-allowed metal-to ligand charge transfer ( MLCT) transitions, an
intense absorption bands at around 250-280 nm and relatively weak absorption at
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90-450 nm were observed. The addition of H PO anions (100 equiv.) did not induce
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any significant change in its UV-vis absorption as shown in Fig. S1. Fig. 1 shows the
photoluminescence properties of iridium (III) complex 1. The iridium (III) complex 1
exhibited phosphorescence with a maximum wavelength of 560 nm in acetonitrile

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upon excitation at 372 nm. To explore the anion selectivity of the iridium (III)
complex 1, binding experiments were performed using tetrabutylammonium salts of
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F , Cl , Br , I , CH COO , and H PO (Fig. 1a). The addition of H PO (100 equiv.)
3
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4
resulted in an enhancement of the phosphorescence of iridium (III) complex 1 with a
4 nm blue shift (Fig. 1b), which could also be observed by the naked eye (Fig. 2).
From the phosphorescence titration experiments of iridium (III) complex 1 (10 μM)
1
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with H PO , the association constant were calculated to be 1.06  10 M .
2
4
Insert Figure 1
Insert Figure 2
If the receptor was connected to the ligand through a spacer, the interaction of the
receptor with the analyte may perturb the energy levels of the excited states [3a]. Thus
-
the phosphorescence enhancement of iridium (III) complex 1 with H PO can be
2
4
attributed to the moderate increase in the energy level of the triplet excited state which
was demonstrated by the 14 nm blue shift of phosphorescence. This increases the
intersystem crossing efficiency and enhances the triplet quantum yield, thus inducing
a “switch on” of the emission.
-
We also investigated the phosphorescence lifetime variation with H PO . The
2
4
system for nanosecond phosphorescence lifetime spectroscopy is illustrated in Fig. S2.
As shown in Fig. 2b, the phosphorescence lifetime of complex 1 increased markedly
-
4
upon the addition H
PO
. The phosphorescence lifetime of complex 1 changed from
2
-
0
.34 s to 0.6 s as the H PO concentration increased from 0.0 to 200.0 M.
2
4

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.2. Chiral recognition of iridium (III) complex 2
Then, Iridium (III) complex 2 was examined for chiral recognition with tetrabutyl
ammonium salts of t-Boc-amino acids and 3,5-dinitrobenzoyl (DNB)-amino acids,
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such as alanine (Ala), valine (Val), threonine (Thr), leucine (Leu), phenylglycine
(Phg) and phenylalanine (Phe). Phosphorescence titrations of iridium (III) complex 2
(10 μM) with D- and L-t-Boc-amino acid derivatives in acetonitrile are illustrated in
the supporting informations. Iridium (III) complex 2 showed phosphorescence
enhancement with t-Boc-amino acid derivatives. Based on phosphorescence titrations
data of iridium (III) complex 2 with t-Boc-amino acid derivatives, the association
constants (K) were calculated according to the linear Benesi-Hildebrand expression
1
7
(Table 1). In general, iridium (III) complex 2 showed larger K values for D-t-Boc
a
amino acid derivatives than those for L-isomers. For example, the association
5
constant of 2 with D- and L-t-Boc-leucine were calculated as 1.10  10 and 3.48 
4
-1
1
0 M , respectively, with the K /K of 3.16.
D L
Insert Table 1
Compared to the t-Boc series, iridium (III) complex 2 displayed phosphorescence
quenching effects with DNB derivatives. The phosphorescence titrations of iridium
(III) complex 2 (10 μM) with D-DNB-threonine and L-DNB-threonine in acetonitrile
are also illustrated in the supporting informations. L-DNB-threonine induced larger

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phosphorescence quenching effect than D-isomer. The phosphorescence quenching
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effects of Iridium complex 2 can be attributed to the -NO group of DNB [11d]. The
2
association constants with DNB-amino acid derivatives were summarized in Table 2.
As shown in Table 2, iridium (III) 2 showed larger K values for L-DNB-amino acid
a
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derivatives. The Job`s plot experiment indicated a 1:1 formation between amino acids
and hosts (Fig. S3).
Insert Table 2
4. Conclusion
In conclusion, here, we report the first example of phosphorescence chemosensor
-
for H PO . Iridium (III) complex 1 contained two preorganized urea groups for the
2
4
-
recognition of H PO . Methylene linkers between bipyridine and urea moieties in
2
4
probe 1 not only provided a nice binding pocket for the selective recognition of
-
-
H PO but also resulted in a higher phosphorescence enhancement with H PO ,
2
4
2
4
which can be compared to the phosphorescence quenching effects of reported iridium
(III) complexes bearing the urea group directly on the benzene. A new chiral
phosphorescent iridium (III) complex 2 bearing two preorganized thiourea groups as
binding sites and two GITC groups as chiral barriers was studied for the recognition
of the α-amino acid derivatives. In addition, bis(benzylic amine) derivative 6 holds
great promise for use as a valuable platform for the development of new
phosphorescence chemosensors through the introduction of various binding sites.

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Acknowledgments
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This research was supported by the National Research Foundation of Korea(NRF)
grant funded by the Korea government(MEST) (No. 2012-0002571 for M.H.H. and
National Creative Research Initiative: No. 2012R1A3A2048814 for J.Y.)
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Scheme Title and Captions of Figures
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Scheme 1. Synthesis of iridium (III) complex 1 and 2.
Figure 1. (a) The phosphorescence spectra of iridium (III) complex 1 (10 M) upon
addition of different anions (10 eq) in CH CN. (b) The phosphorescence titration
spectra of iridium (III) complex 1 (10 M) upon addition of tetrabutyl ammonium
3
dihydrogenphosphate in CH CN. Excitation wavelength: 372 nm.
3
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Figure 2. (a) Phosphorescence changes iridium (III) complex 1 by naked-eye upon
the addition of tetrabutyl ammonium dihydrogenphosphate in CH CN. Excitation
3
wavelength: 365 nm. (b) The phosphorescence lifetime of iridium (III) complex 1 (20
-

M) and 1 with H PO (10 eq.) in CH CN.
2
4
3
-1
Table 1. The association constants (M ) of iridium (III) complex 2 with
t-Boc-amino acid derivatives in acetonitrile.
-1
Table 2. The association constants (M ) of iridium (III) complex 2 with
DNB-amino acid derivatives in acetonitrile.

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Scheme 1. Synthesis of iridium (III) complex 1 and 2.

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Figure 1. (a) The phosphorescence spectra of iridium (III) complex 1 (10 M) upon
addition of different anions (10 eq) in CH CN. (b) The phosphorescence titration
spectra of iridium (III) complex 1 (10 M) upon addition of tetrabutyl ammonium
3
dihydrogenphosphate in CH CN. Excitation wavelength: 372 nm.
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Figure 2. (a) Phosphorescence changes iridium (III) complex 1 by naked-eye upon
the addition of tetrabutyl ammonium dihydrogenphosphate in CH CN. Excitation
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Table 1. The association constants (M ) of iridium (III) complex 2 with
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K (M )
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Valine
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.83  10
Threonine
Alanine
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3.52  10
1.32
2.05
Phenylalanine
-1
Table 2. The association constants (M ) of iridium (III) complex 2 with
DNB-amino acid derivatives in acetonitrile.
-1
-1
Guest
Phenylglycine
Leucine
K (M )
K / K
K (M )
D
L
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2.95  10
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2.60  10
0.88
1.73
1.25
3.04
1.19
2.25
1.53  10
5.11  10
5.82  10
1.54  10
3.68  10
5.85  10
Valine
Threonine
Alanine
Phenylalanine

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Graphical Abstract
New Iridium Complexes with Two Pre-organized Urea Groups
and Thiourea Groups as Phosphorescent Chemosensors for
1
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-
H
PO
and Chiral Carboxylates
2
4
Yinan Li, Liu Yifan, Dayoung Nam, Sungnam Park, Juyoung Yoon* and Myung Ho
Hyun*
Highlights



As a versitle platform for phosphorescent chemosensors, bis(benzylic amine)
derivative 6 was synthesized.
A phosphorescent chemosensor 1 displayed a selective phosphorescence
-
4
enhancement with H PO .
2
A new iridium complex 2 is reported as a first chiral phosphorescent
chemosensor for amino acids.

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Supporting Informations for
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New Iridium Complexes with Two Pre-organized Urea
Groups and Thiourea Groups as Phosphorescent
-
Chemosensors for H PO and Chiral Carboxylates
2
4
1
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a†
b†
c
c
b
Yinan Li, Liu Yifan, Dayoung Nam, Sungnam Park, Juyoung Yoon * and Myung
a
Ho Hyun *
a
Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National
University, Busan 690-735, Korea
b
Department of Chemistry and Nano Science, Ewha Womans University, Global Top5
Research Program, Seoul, 120-750, Korea
c
Department of Chemistry, Korea University, Seoul, 136-701, Korea
jyoon@ewha.ac.kr; mhhyun@pusan.ac.kr
† equally contributed to this work
Figure S1 UV-vis spectra and phosphorescence spectra of complex 1 ..........................................S9
Figure S2 System for phosphorescence life time measurements..................................................S13
Figure S3 Job`s plot of complex 2 and t-Boc-D-Leucine amino acid . ........................................S14
Figure S4 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-D-valine. .....................S15
Figure S5 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-L-valine.......................S16
Figure S6 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-D-leucine.....................S17
Figure S7 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-L-leucine.....................S18
Figure S8 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-R-phenylglcine...........S19
Figure S9 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-S-phenylglcine ............S20
Figure S10 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-L-threonine ..............S21
Figure S11 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-D-alanine...................S22
Figure S12 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-L-alanine...................S23
Figure S13 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-D-phenylalanine.......S24
Figure S14 GITC appended iridium (III) complex 2 (10 μM) with t-Boc-L-phenylalanine ........S25
Figure S15 GITC appended iridium (III) complex 2 (10 μM) with DNB-D-valine.....................S26

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Figure S16 GITC appended iridium (III) complex 2 (10 μM) with DNB-L- valine ...................S27
Figure S17 GITC appended iridium (III) complex 2 (10 μM) with DNB-D-leucine...................S28
Figure S18 GITC appended iridium (III) complex 2 (10 μM) with DNB-L-leucine ...................S29
Figure S19 GITC appended iridium (III) complex 2 (10 μM) with DNB-R-phenylglycine ........S30
Figure S20 GITC appended iridium (III) complex 2 (10 μM) with DNB-S-phenylglycine.........S31
Figure S21 GITC appended iridium (III) complex 2 (10 μM) with DNB-D-threonine ...............S32
Figure S22 GITC appended iridium (III) complex 2 (10 μM) with DNB-L-threonine................S33
Figure S23 GITC appended iridium (III) complex 2 (10 μM) with DNB-D-alanine...................S34
Figure S24 GITC appended iridium (III) complex 2 (10 μM) with DNB-L-alanine ...................S35
Figure S25 GITC appended iridium (III) complex 2 (10 μM) with DNB-D-phenylalanine ........S36
Figure S26 GITC appended iridium (III) complex 2 (10 μM) with DNB-L-phenylalanine.........S37
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Figure S1. UV-vis spectra and phosphorescence spectra of iridium (III) complex 1 (10 μM) in
acetonitrile.
Nanosecond Photoluminescence Spectroscopy
DigitalOscilloscope
Trigger
Ch.1
Ch.2
Nd:YAG laser
355 nm & 5 ns)
(
P
Polarizer
FastPre-Amp
Signal
M
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Sample
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Monochromator
Time resolution = 16.6
Figure S2. System for phosphorescence life time measurements.

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Figure S3. Job`s plot of complex 2 and D-t-Boc-Leucine amino acid in acetonitrile.

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Figure S4. (a) The phosphorescence titration spectra of GITC appended iridium (III) complex
(10 μM) upon addition of t-Boc-D-valine in 100 % CH CN. (b) Benesi-Hildebrand plot of
2
3
PL spectra of complex 2.