Cyclometalated Ir(III) Complex as a Metalloligand and a. Selective Cu(II) Sensor: Synthesis and Structural

Transcription

1 Supporting Information Cyclometalated Ir(III) Complex as a Metalloligand and a Selective Cu(II) Sensor: Synthesis and Structural Characterization of a Heterometallic Tetranuclear Ir(III)/Cu(II) Complex Vadapalli Chandrasekhar* [a][b], Bani Mahanti [a], Mrituanjay D. Pandey [c], and R. Suriya Narayanan [b] [a] Prof. Dr. V. Chandrasekhar and Dr. Bani Mahanti Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur , India. vc@iitk.ac.in [b] Prof. Dr. V. Chandrasekhar and Dr. R.Suriya Narayanan Tata Institute of Fundamental Research, Hyderabad , India. vc@tifrh.res.in [c] Dr. Mrituanjay D. Pandey Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi, UP , India. CORRESPONDING AUTHOR FOOTNOTE: * To whom correspondence should be addressed. vc@iitk.ac.in, vc@tifrh.res.in. Phone: (+91) Fax: (+91) / S1

2 Figure S1: Distorted square pyramidal geometry around the Cu(II) centre in 3 S2

3 4.0 Absorption Ca Cd Cu Hg Mn Ni Pb Zn Wavelength (nm) Figure S2: Absorption spectra of 2 (10.0 µm) and after addition of various metal perchlorates (100.0 µm) in acetonirile [(A-A O )/A O ] Mole Fraction of [Cu(II)] Figure S3: Jobs plot for the binding of 2 with Cu 2+ showing the formation of a complex with 1:1 stoichiometry. S3

4 a) Hg (2.5 µm) Hg (5 µm) Hg (10 µm) Hg (20 µm) Hg (40 µm) Hg (70 µm) Hg (100 µm) Absorption Pb (2.5 µm) Pb (5 µm) Pb (10 µm) Pb (20 µm) Pb (40 µm) Pb (70 µm) Pb (100 µm) b) Wavelength (nm) Figure S4: Absorption spectra of 2 (10.0 µm in acetonitrile upon addition of increasing concentrations of Hg 2+ (a) and Pb 2+ (b). S4

5 Intensity (au) A B C D E F G H Contents Figure S5: Phosphorescence response of 2 (10µM) in acetonitrile in the presence of a mixture of metal ions. The concentration of metal ions was 10 µm. Where; A = 2, B = 2 Cu, C = 2 Cu+Cd, D = 2 Cu+Hg, E = 2 Cu+Pb, F = 2 Cu+Zn, While G = 2 Cu+EDTA (5µM), H= 2 Cu+EDTA (10µM). Disodium salt of EDTA was taken in water. Fluorescence Intensity (a.u.) [Cu 2+ ] (µm) Figure S6: Plot of emission intensity as a function of Cu 2+ concentration. S5

6 50 40 Intensity (au) Wavelength (nm) Figure S7: Emission spectrum of 3 (1uM) in acetonitrile solution. 1.5 Absorption F - Cl - Br - I - PF Wavelength (nm) Figure S8: Absorption spectra of compound 2 (10.0 µm) and after addition of various anions (100.0 µm) in acetonitrile. S6

7 Intensity (au) F - Cl - Br - I - PF Wavelength (nm) Figure S9: Emission spectra of compound 2 (10.0 µm) and after addition of various anions (100.0 µm) in acetonitrile. The excitation wavelength was kept at 350 nm. S7

8 HOMO LUMO HOMO-1 LUMO+1 HOMO-2 LUMO+2 Figure S10: Relevant molecular orbitals of 2 (iso value=0.04) obtained from DFT calculations. S8

9 Figure S11: Normalised experimental and calculated UV-Vis spectra of 2. The singlet excited states are shown as green vertical bars with height equal to the oscillator strength. (Calculated spectra obtained using program GAUSSUM S9

10 Table S1: Molecular Orbital composition (%) in the ground state at the PBE0/LANL2DZ/6-31G(d) level for 2 (LC= Cyclometalating ligand, LA=Ancillary ligand). Orbital Energy (ev) Main bond nature LUMO L C (22.8%) + L A (75%) LUMO L C (48.2%) + L A (47.3%) LUMO L C (29.7%) + L A (65.6%) LUMO L C (89.9%) + L A (5.8%) HOMO Ir-d (21.1%)+ L C (12.2%) + L A (65.6%) HOMO Ir-d (40.5%) + L C (43.5%) + L A (15.4%) HOMO Ir-d (21.1%) + L C (12.4%) + L A (65.5%) HOMO L C (20.5%) + L A (77.7%) Table S2: Singlet excited states calculated at the PBE0/LANL2DZ/6-31g(d) level using pcm solvation model for molecule 2 (LC= Cyclometalating ligand, LA=Ancillary ligand). States Participating MO E(eV) λ (nm) f Transition Character S1 HOMO LUMO (74%) Ir(d)+ L A + L C L C HOMO LUMO+1 (15%) Ir(d)+ L A + L C L A + L C S2 HOMO LUMO+1 (65%) Ir(d)+ L A + L C L A + L C HOMO LUMO (16%) Ir(d)+ L A + L C L C S3 HOMO LUMO+2 (72%) Ir(d)+ L A + L C L C +L A HOMO LUMO+3 (17%) Ir(d)+ L A + L C L A + L C S4 HOMO LUMO+3 (46%) Ir(d)+ L A + L C L A + L C HOMO 1 LUMO (32%) HOMO LUMO+2 (10%) Ir(d)+ L C +L A L C Ir(d)+ L A + L C L C +L A S5 HOMO 1 LUMO+1 (46%) Ir(d)+ L C +L A L A + L C HOMO 1 LUMO (25%) HOMO LUMO+3(12%) Ir(d)+ L C +L A L C Ir(d)+ L A + L C L A + L C S10

11 Table S3: triplet excited states calculated at the PBE0/LANL2DZ/6-31g(d) level using pcm solvation model for molecule 2 (LC= Cyclometalating ligand, LA=Ancillary ligand). States Participating MO E(eV) λ (nm) f Transition Character T1 HOMO LUMO (55%) Ir(d)+ L A + L C L C T2 HOMO LUMO +2(21%) Ir(d)+ L A + L C L C +L A HOMO LUMO+1(19%) HOMO 1 LUMO (17%) Ir(d)+ L A + L C L A + L C Ir(d)+ L C +L A L C Table S4: Photophysical data of 3. λ max, nm (ε; 10 4 ) λ em, nm Φ (30.0), 356 (7.2), 429 (2.0) Table S5. Olex-2 mask details Compound Masked electron count Calculated solvent(s) CH 2 Cl 2 and 0.5 CH 3 OH (120) CH 2 Cl 2 and 0.5 CH 3 OH (93) S11