SUPPELEMENTARY DATA Sensitivity of Mercury(II) … · Aggregation Induced Emission (AIE) Active Iridium ... with Appended Phosphine Based Fluorescent Sensor: High Sensitivity of Mercury(II)

SUPPELEMENTARY DATA

Aggregation Induced Emission (AIE) Active Iridium(III) Complex with Appended Phosphine Based Fluorescent Sensor: High Sensitivity of Mercury(II) IonsParvej Alama, Gurpreet Kaurb, Clàudia Climentc, Saleem Pashaa, David Casanovad, Pere Alemanyc*, Angshuman Roy Choudhuryb*, Inamur Rahaman Laskara*

aDepartment of Chemistry, Birla Institute of Technology and Science, Pilani Campus, Pilani, Rajasthan, India, [email protected]; bDepartment of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Mohali, Sector 81, S. A. S. Nagar, Manauli PO, Mohali, Punjab, 140306, India, [email protected]; cDepartament de Química Física and Institut de Química Teòrica i Computational (IQTCUB), Universitat de Barcelona. Martí i Franquès 1-11, 08028 Barcelona, Spain, Email: [email protected]; dKimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), Donostia International Physics Center (DIPC), P.K. 1072, 2080 Donostia, Spain; and IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain.

a

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2014

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c

Fig. S1. 1H and 31P NMR spectra clearly showing the mixture of cis-C,C- and trans-C,C-isomers of bis-2-(2,4-difluorophenyl)pyridine(diphosphine)iridium(III) complexes with iridium(III) (a,b); HRMS spectrum of the same mixture are shown (c).

a

b

C

d

Fig. S2 (1H, 31P, 19F)NMR spectra and HRMS (a, b, c and d), respectively for 1.

d

Fig. S3 (1H, 31P, 19F)NMR spectra (a, b, c and d), respectively for complex 2.

a

B

Fig. S4 (1H and 31P) NMR and HRMS spectra (a ,b and c), respectively for complex 3.

a

b c

Fig. S5 (a) PL spectra of complex 2 with [M] =10-5 mol L-1 in DMF–water mixtures with different water fractions (fw). (b) Fuorescent photographies of the aqueous mixtures taken under a 365 nm UV lamp with different fw values. (c) Solid state emission for complex 2.

Fig.S6 Comparative solid state and solution (10−4 M, DCM) photoluminescence spectra for complexes 1 and 2 [ peaks in solution: (461 and 488 nm), peaks in solid: (468 and 503 nm) respectively].

a

b

Fig.S7 (a) PL spectra of complex 1 with [M] =10-5 mol L-1 in DMF–PEG mixtures , PEG fraction (fPEG ) (b) PL spectra of complex 2 with [M] =10-5 mol L-1 in DMF–PEG mixtures, PEG fraction (fPEG ).

Fig. S8 Absorption spectra of complexes 1 and 2 in DMF/water mixtures with different water fractions ( fw).

Fig. S9 PXRD data for complexes 1 and 2 showing the partial crystaline and amorphous nature of the complexes, respectively.

a b

Fig. S10 Photoluminescence lifetime decay curves (a) in DMF and (b) in 7:3 (Water : DMF) for complex 1 and (c)

in DMF and (d) in 9:1 (Water : DMF) for complex 2 (the red line is the fitting curve).

a b

Fig. S11 (a,b) . Particle size distribution of nano-aggregates of complexes 1 and 2 formed in a DMF / water mixture

with a 90% water fraction.

Fig. S12 Emission and absorption spectra for complex 3 in DMF (10-5M)

Fig. S13 Response of complex 2 to the presence of Hg+2 in a DMF / water mixture with a 90% water fraction.

Fig. S14 Absorption response of complex 1 in the presence of various metal cations (4 eq.) in a (7:3)v/v Water : DMF mixture.

Fig. S15 Changes in the UV–VIS absorption spectrum of 1 with a gradual variation of the Hg+2 concentration (0 -14 μM)

Fig. S16 Absorbance change (ΔA = A0 – A) of complex 1 at 340 nm in a 7:1 water: DMF mixture, methanol buffered, in the presence of 0 – 14 μM of Hg+2. The solid line is the theoretical 1:1 binding curve of ΔA vs. [Hg+2].

a

b

c

(i) (ii)

(iii)

d

Fig.S17 (a) 1H NMR spectra of PPh2 ligand and complex 1 with Hg+2 in d6 DMSO. (A) only complex 2; (B) complex 2 + Hg+2 (2.0eq ) ; (C) PPh2 ligand+ Hg+2 (2.0eq ) (D) PPh2 ligand, (b) 31P NMR spectra of PPh2

ligand and complex 2 with Hg +2 in d6 DMSO. (A) only complex 2; (B) complex 2 + Hg+2 (2.0eq ) ; (C) PPh2 ligand + Hg+2 (2.0eq ) (D) PPh2 ligand. (c) HRMS spectra of 1 after using 2 equivalent of Hg+2 (d) (i) only Hg(NO3)2, 1380 cm-1 (ii) PPh2 ligand, 1482, 1299 and 1225 cm-1 (iii) PPh2 + 2 equivalents of Hg+2, 1481, 1434, 1380, and 1280 cm-1

a

b

c

d

Fig. S18 (a, b, c and d). 31P, IR, HRMS and 19F NMR spectra of 4, respectively.

Table S1 Photophysical Parameters for complexes 1 and 2

Complex UV-Vis absorptiona nm, ( ε,M-1cm-1)

PLb (( emi) (nm)

PLc (( emi) (nm)

(ns)d (μs)e QYf (%) (ϕ solution)

QYg (%) (ϕ solid)

1 254 (60190), 307(17333), 370(4333), 469(103)

461,488 463,504 19.30 2.00 0.067 7.252

2 253(68571), 302(25857), 371(6714), 450(247)

461,488 468,504 55.19 3.38 0.020 6.165

3 253(67450), 302(24350), 371(6580), 450(197)

461,488

a Spectra were recorded in degassed dichloromethane (DMF) at room temperature with ε x10-5 M-1cm-1; b recorded in DMF ; cthin film emission; d life time was measured in DMF, eaggregated form of the complexes resulted in water-DMF mixtures (9:1) fw= 70% for complex 1 and 99 % for complex 2 fquantum yields for the two complexes were measured in degassed DMF against quinine sulfate in 1.0 N sulfuric acid as reference (QY = 0.546). gSolid state phosphorescence QE (ϕ solid) has been recorded using integrating sphere

Table S2. Geometrical parameters for the coordination environment of Iridium in the optimized ground state

structures of compounds 1 and 2 in dichloromethane solution.

Bond distances(a), Å Angles (º)

Complex Ir-N Ir-C Ir-Cl Ir-P N-Ir-N C-Ir-C Cl-Ir-P

1 2.091 2.025 2.589 2.582 170.0 89.9 90.2

2 2.094 2.026 2.571 2.608 169.9 88.2 89.5

(a) Average value of the two Ir-X distances in each compound.

Table S3. Selected Frontier Molecular orbitals of complexes 1 and 2

HOMO-2 HOMO LUMO LUMO+1

Complex 1

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Table S4. Vertical excitation energies and oscillator strengths calculated for the transition to the first excited singlet

state for the two studied complexes.

Complex ΔE, eV (nm) Osc. Str. %HOMO-LUMO EHOMO, eV ELUMO, eV

1 3.26 (380) 0.037 95 -5.68 -1.64

2 3.19 (389) 0.032 97 -5.64 -1.69

Table S5. MLCT character for the transitions from the ground state (S0) to the first and fourth excited singlet (S1,

S4) and triplet states (T1).

Complex S0 S1 S0 S4 S0 T1

1 43% 46% 14%

2 45% 48% 20%