Piezoflurochromism and Aggregation induced Emission properties of 9, 10-bis (trisalkoxystyryl) anthracene derivatives

Kumaraguru Duraimurugan,a Jayaraman Sivamani,a Munusamy Sathiyaraj,b Viruthachalam Thiagarajanb and Ayyanar Sivaa*

aSchool of Chemistry, Madurai Kamaraj University, Madurai-625 021, Tamilnadu, India.

bSchool of Chemistry, Bharathidasan University, Trichirapalli-24, Tamilnadu, India

Corresponding author:

Contents

1.  Materials and characterization 2

2.  Thermal, UV, PL spectra 3-5

3.  Pfc and CV Spectra 6

4.  NMR, HRMS spectra 7-18

1.  Materials and Methods

All the chemicals were directly used for the synthesis without further purification unless otherwise stated. Methyl-3, 4, 5-Trihydroxy benzoate, lithium aluminium hydride, methyl triphenylphosphoniumbromide, pyridiniumchlorochromate, tetrabutylammoniumbromide, N-bromosuccinimide, 9,10-dibromo anthracene and Pd(OAc)2 were purchased from Aldrich. 1-bromooctane and 1-bromododecane were purchased from Alfa Aesar. Solvents for chromatography and crystallization were distilled once before use. Technical grade solvents were used for extraction. Dry THF were distilled from Sodium/Benzophenone and dry DCM was distilled over Calcium hydride and stored on KOH pellets.

Characterization

Bruker (300MHz) instrument were used to record 1H NMR &13C NMR spectra. Chemicals shift (δ) is reported in parts per million (ppm) relative to residual solvent peaks or tetramethylsilane, and coupling constants are reported in Hertz (Hz). NMR solvents were obtained from Merck. The spectra were recorded at Room Temperature. The multiplicities were denoted s= singlet, d=doublet, t=triplet, q=quartet, m=multiplet. Silica gel-G plates (Merck) were used for TLC analysis with a mixture of n-hexane and ethyl acetate as an eluent. Column chromatography was carried out in silica gel (60-120 mesh) using n-hexane and ethyl acetate as an eluent. UV absorption was measured in JASCO V-630, Spectroflurometer was measured in Agilent 8000 and FT-IRwas recorded in a JASCO FT/IR-410 spectrometer. KBr used as pellets. High resolution mass spectrometry was recorded in Jeol-AccuTOF. The THF/Water mixtures with different water fractions were prepared by slowly adding distilled water into THF solutions of the sample under ultrasound at RT. Cyclic voltammetry was carried out using CHI 680 electrochemical working station at RT with scan rate of 100 mV s-1. Transmission electron microscopy (TEM) images were observed using TECHNAI T20 instruments at accelerating voltages of 200 and 5 kV, respectively. Samples were prepared by drop casting of dilute aggregate dispersions onto copper 400-mesh carrier grids covered with carbon-coated Formvar films. The solvent was evaporated at room temperature in open air. The ground-state geometries were optimized using density functional theory with B3LYP hybrid Functional at the basis set level of 6-31G. All the calculations were performed using Gaussian 03 package. Nanoaggregate sample was prepared by the following method. A stock solution of C8-Ant and C12-ant in THF with the predetermined concentration of 1x10-3M was prepared. Aliquots of the samples were transferred into 5mL volumetric flask. After adding appropriate amount of THF, water was added dropwise under vigorous stirring to furnish 1x10-5 M solutions with different water fractions. The absorption and emission spectra of these resultant mixtures were measured immediately.

Fig S1: TGA spectrum of C8-ant and C12-ant

Fig S2: DSC spectrum of C8-ant and C12-ant

Fig S3: Absorption and Emission spectra ofC12-ant in different solvents.

Fig S4. The images of C8-ant (a) & C12-ant (b) in solid form and THF solution under the illumination of 365 nm

Fig S5: plot of PL intensity Vs different water fractions of C8-ant

Fig S6: UV and PL spectra of C12-ant in various THF/water mixtures at 1x 10-5M concentrations. Inset pictures show non-emissive (0%) and emissive (50%) in different THF –water fractions.

Fig S7: TEM image of nanoaggregates of C12-ant in THF/water mixture at 60% and electron diffraction pattern (a) Formation of particles (b) Selected area electron diffraction pattern.

Entry / Original / pressed / Annealed / λpfc(Original-Pressed)
C8-ant / 535nm / 546nm / 577nm / 11nm
C12-ant / 531nm / 552nm / 590nm / 30nm

Fig S8: Peak emission wavelengths (λ, in nm) of Cn-ant solids under various external stimuli.

Fig S9: Normalized emission spectra of C12-ant solids of different conditions (excitation at 413nm).

Entry / Eonset (V) / Ep1ox (V) / Ep2ox (V) / HOMO (eV) / LUMO (eV) / Eg (eV) / Calculated
Eg (eV)
C8-ant
C12-ant / 0.68
0.69 / 0.81
0.82 / 1.07
1.08 / -5.28
-5.29 / -2.70
-2.65 / 2.58
2.64 / 2.94
2.98

Fig S10: HOMO and LUMO values of C8-antC12-ant in DCM solution calculated by Cyclicvoltammogram and theoretical calculated values.

Fig S9: 1H NMR Spectrum of Methyl-3,4,5-Tris-octyloxy-benzoate (2a).

Fig S10: 13C NMR Spectrum of Methyl-3,4,5-Tris-octyloxy-benzoate (2a).

Fig S11: 1H NMR Spectrum of (3,4,5-Tris-octyloxy-phenyl)-methanol (3a).

Fig S12: 13C NMR Spectrum of (3,4,5-Tris-octyloxy-phenyl)-methanol (3a).

Fig S13: 1H NMR Spectrum of 3,4,5-Tris-octyloxy-benzaldehyde (4a).

Fig S14: 13C NMR Spectrum of 3,4,5-Tris-octyloxy-benzaldehyde (4a).

Fig S15: 1H NMR Spectrum of 1,2,3,-Tris-octyloxy-5-vinyl-benzene (5a).

Fig S16: 13C NMR Spectrum of 1,2,3,-Tris-octyloxy-5-vinyl-benzene (5a).

Fig S17: HRMS Spectrum of9,10-Bis-[2-(3,4,5-tris-octyloxy-styryl)]-anthracene (7)

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Fig S18: 1H NMR Spectrum of 9,10-Bis-[2-(3,4,5-tris-octyloxy-styryl)]-anthracene (7)

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Fig S19: 13C NMR Spectrum of 9,10-Bis-[2-(3,4,5-tris-octyloxy-styryl)]-anthracene (7)

Fig S 20: 1H NMR Spectrum of Methyl-3,4,5-Tris-dodecyloxy-benzoate (2b)

Fig S 21: 13C NMR Spectrum of Methyl-3,4,5-Tris-dodecyloxy-benzoate (2b)

Fig S22: 1H NMR Spectrum (3,4,5-Tris-dodecyloxy-phenyl)-methanol (3b)

Fig S23: 13C NMR Spectrum of (3,4,5-Tris-dodecyloxy-phenyl)-methanol (3b)

Fig S24: 1H NMR Spectrum of 3,4,5-Tris-dodecyloxy-benzaldehyde (4b).

Fig S25: 1H NMR Spectrum of 3,4,5-Tris-dodecyloxy-benzaldehyde (4b).

Fig S26: 1H NMR Spectrum of 1,2,3,-Tris-dodecyloxy-5-vinyl-benzene (5b)

Fig S27: 13C NMR Spectrum of 1,2,3,-Tris-dodecyloxy-5-vinyl-benzene (5b)

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Fig S28: HRMS Spectrum of 9,10-Bis-[2-(3,4,5-tris-dodecyloxy-styryl)]-anthracene(8)

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Fig S29: 1H NMR Spectrum of 9,10-Bis-[2-(3,4,5-tris-dodecyloxy-styryl)]-anthracene(8)

Fig S30: 13C NMR Spectrum of 9,10-Bis-[2-(3,4,5-tris-dodecyloxy-styryl)]-anthracene(8)

8