1
Supporting Information
Photochromic Conjugated Microporous Polymer Manifesting
Bio-inspired pcFRET and Logic Gate Functioning
Ashish Singh, Parul Verma, Subhajit Laha, Debabrata Samanta, Syamantak Roy and Tapas Kumar Maji*
Molecular Materials Laboratory, Chemistry and Physics of Material Unit, School of Advance Material (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore-560064, India
*Email: [email protected]
Tel: 91-8022082826
Table of Content
Page NoPhysical Measurements 2-3
Experimental Section 3
Materials 3
Quantum yield measurement for photoisomerization 4-5
Electrical conductivity 5
Cyclic Voltammetry (CV) experiment 6
Fluorescence lifetime (τ), energy transfer efficiency (Φe) and energy transfer constants (ke)
2
Physical Measurements:
Infrared spectra (IR) were recorded in Bruker FT-IR spectrometer. Samples were prepared as pellet
using KBr for IR measurement. The thermal stability was measured in Mettler Toledo-TGA 850
instrument under N2 atmosphere within the temperature range 30 – 800 °C at a heating rate of 5
°C/min. Elemental analysis was performed in Thermo Scientific Flash 2000 CHN analyser.
Powder X-ray diffraction for pcCMP was recorded in Bruker D8 discover instrument using
Cu-K∝ radiation. Morphological studies were carried out using Lica-S440I Field Emission Scanning
Electron Microscope (FESEM) by placing samples on a silicon wafer under high vacuum with an
accelerating voltage of 100 kV. Transmission Electron Microscopy (TEM) analyses were
performed using JEOL JEM-3010 with an accelerating voltage at 300 kV. Energy dispersive
spectroscopy (EDS) analysis was performed with an EDAX genesis instrument attached to the
FESEM column. Solid-state 13C-NMR spectra were recorded in Varian infinity plus 300WB
spectrometer at a MAS rate of 5 kHz with a CP contact time of 1.4 ns. Adsorption measurements
Synthesis 7
(a) Synthesis of
4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophe -ne-2-carbaldehyde) (DTE-dialdehyde) 7 (b) Synthesis of benzene-1,3,5-tricarbohydrazide 7-8
(c) Synthesis of gfp chromophore analogue (gfp-I) 8
(d) Encapsulation of gfp-I in the pcCMP-O (pcCMP-O-gfp-I) 9
DFT Study 9-16
Characterization data for pcCMP and pcCMP-gfp-I 17-24
NMR spectra 25-27
3
(N2 (77 K) and CO2 (195 K)) were carried out in a QUANTACHROME QUADRASORD-SI
analyser. The polymer pcCMP was degassed at 160 °C under 1×10-1 Pa vacuum for 15 hrs before
the sorption measurement. Whereas gfp chromophore encapsulated CMP, pcCMP-O-gfp-I was
degassed at 70 °C for 8 h prior to sorption study. Methanol solvent adsorption measurement has
been carried out at 293 K in the vapour state using BELSORP-aqua-3 volumetric adsorption
instrument. UV-Vis studies were performed using Perkin Elmer Model Lambda 900
spectrophotometer instrument. The photoluminescence properties were performed in Fluorolog
3.21 spectrofluorimeter (Horiba Jobin-Yvon) instrument. Fluorescence decay profiles were
recorded in a time-correlated single photon counting spectrometer of Horiba-Jobin Yvon with 350
– 450 nm picosecond Ti-saphhire laser with 370 nm.
Experimental Section:
Materials:
Chemicals used for the synthesis of DTE- dialdehyde and gfp-I chromophore were procured from Sigma-Aldrich chemical Co. Ltd and used as such. All solvents were purchased from Spectrochem Pvt. Ltd. India. Tetrahydrofuron (THF) and dimethyl-formamide (DMF) solvents were dried using reported procedure before using in the reactions.1 Hydrazine, 1,3,5-tricarboxylic acid and
potassium carbonate were obtained from Spectrochem Pvt. Ltd. India and used as such. All the photophysical studies and CV experiment were carried out using HPLC grade solvents. For column chromatography, solvents were purchased from Finar Ltd, India and used as such. Deuterated chloroform (CDCl3) was purchased from Sigma-Aldrich chemical Co. Ltd and used for 1H and 13C-NMR as such.
4
Quantum efficiency for photoisomerization (open→close and close→open) and %
conversion from pcCMP-O to pcCMP-C:
Quantum yield for photo-isomerization reaction. Sample for quantum yield measurement was
prepared by making a thin film of pcCMP-O via spin coating.2 The thickness of film was found to be 975 nm. The quantum yield for photo-isomerization of pcCMP from open→close and close→open was calculated upon irradiating with 365 nm and 550 nm light, respectively. Quantum yield for photocyclization (pcCMP-O to pcCMP-C) and photo-cycloreversion (pcCMP-C to pcCMP-O) were calculated using the following equation;
Φ
𝑥=
∆𝐴/∆𝑡
(𝑁ℎ𝑣/𝑡) × 𝜀
𝑥× 𝐹
𝑥Where ΔA/Δt is the change in absorbance at a particular wavelength upon irradiation. Slope was calculated from time-dependent UV-Vis absorption spectra (Figure S22) for photocyclization (ΔA/Δt= 0.0017) and for photocycloreversion (ΔA/Δt= 0.00026). εx is the molar extinction
coefficient at a particular wavelength (ε632 nm = 7378 M−1 cm−1 for pcCMP-C and ε307 nm = 6909
M−1 cm−1 for pcCMP-O). Fx is the mean fraction of light absorbed and can be calculated as 1–10
-A. F
x was calculated for maximum absorption for pcCMP-C at 632 nm, 0.52. Fx for open form
corresponding to maximum absorption occurred at 307 nm, calculated as 0.48. Nhv is light intensity used for irradiation (for open→close, 365 nm UV light of 96 μW and for close→open, 550 nm Visible light of 130 μW). The Φc is the quantum yields of photocyclization and Φo represent the quantum yield for cyclo-reversion.
Table S1: Quantum efficiency for pcCMP-O → pcCMP-C and pcCMP-O → pcCMP-C
Photoreaction Φx
pcCMP Open to close Φc = 0.85
pcCMP Close to open Φo = 0.71
Photocyclization conversion ratio measurement. The ratio of the equilibrium concentrations of
the open form (Co) and closed forms (Cc) at a given photostationary state (PSS) is expressed as follows;
5 𝐶𝑜 𝐶𝑐 = 𝜑𝑐 → 𝑜 × 𝜀𝑐 𝜑𝑜 → 𝑐 × 𝜀𝑜= 𝜑𝑐 → 𝑜 × 𝐴𝑐 𝜑𝑜 → 𝑐 × 𝐴𝑜
where εo and εc are the molar absorption coefficients of the open and closed forms,
Ao and Ac represent maximum absorbance for open (pcCMP-O at 307 nm) and closed form (pcCMP-C at 632 nm), Φo→c and Φc→o is quantum yields for cyclization and cyclo-reversion, respectively.
Table S2: Maximum conversion of pcCMP-O → pcCMP-C.
Photoreaction λirr Conversion ratio (PSS)
pcCMP-O to pcCMP-C 365 nm 78 %
Electrical conductivity:
A fine dispersion of 2 mg of pcCMP-O in 0.2 mL THF was made upon sonication and subsequently spin coated on glass surface at 1200 rpm for 60 seconds. Thin film of pcCMP-O on glass surface was dried at 60 °C for 1 hr. Next, aluminium metal (Al) was deposited under vacuum by physical vapour deposition (PVD) method on pcCMP-O coated glass by masking the polymer layer using Teflon-tape. Electrical conductivity was then measured for Al deposited thin film of pcCMP-O and pcCMP-C for several cycles upon signing the visible and UV light, respectively. The conductivity for both photo-isomers, pcCMP-O and pcCMP-C were calculated by following formula;
Conductivity = Slope × ( L WT)
Where L= length of the coated surface, W= width of the coated surface, T= Thickness of the coating.
6
Cyclic Voltammetry (CV) experiment:
The cyclic voltammetry (CV) experiment was performed in Metrohm Autolab Nova 2.1 instrument which is configured with three-electrode cell (glassy carbon (GC) electrode as the working electrode (WE), platinum as a counter electrode (CE) and Ag/AgNO3 as a reference electrode
(RE)). An electro-chemical ink was prepared by making dispersion of 2.5 mg of pcCMP-O in the solvent mixture of isopropanol (500 µl) and water (500 µl). Further, Nafion (14 µl) was added as a binder into the electro-chemical ink. Upon sonication for 30 minutes, a well dispersed ink (3.5 µl) was drop coasted over the GC electrode and allowed to dry for 3 hrs under ambient condition. This was done four times and therefore cumulatively 13.5 µl ink was drop-coasted. The CV experiment was done in the potential range of -1.4 to +1.4 V at the scan rate was 5 mV/s and potential is given in the plot wrt to Ag/AgNO3.
Fluorescence lifetime (τ), energy transfer efficiency (Φe) and energy transfer constants (ke)
The weighted average fluorescence lifetimes were calculated using the following algorithm.3
τav = (Aw1τ1 + Aw2τ2 + Aw3τ3)/(Aw1 + Aw2 + Aw3), where Awi = Ai / ΣAi
τ and A are lifetime and amplitude, respectively, for multi-exponential fitting. Fitting of fluorescence decays. Energy transfer efficiency, Φe.
Φe = ke / (kr + knr + ke) = ke / (ko + ke)
Where kr, knr, and ke = radiative decay, non-radiative decay, and energy transfer constants,
respectively. The ko and ke values were found from the lifetimes of the bare gfp-I and after UV
light irradiation of pcCMP-C-gfp-I, which are τno-ET = 1/ko and τET = 1/(ko + ke), respectively.
τno-ET = 0.128 ns and τET = 0.034 ns.
Hence, ko= 7.81 ns-1 or 7.81 × 10-9 s-1, ke = 21.60 ns-1 or 21.6 × 10-9 s-1
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Synthesis
:
(a)
Synthesis of 4,4'(perfluorocyclopent1ene1,2diyl)bis(5methylthiophe
-ne-2-carbaldehyde) (DTE-dialdehyde):
DTE-dialdehyde has been synthesized and reported earlier by our group.4 Similar synthetic procedure was applied here and characterization data was found to be the similar with the reported one. 1H NMR (400 MHz, CDCl3): 2.03 (s, 6H, CH3), 7.73 (s, 2H, ArH), 9.84 (s, 2H, CHO). 13C NMR (100 MHz, CDCl3):15.4, 125.8, 135.6, 142.2, 151.6, 181.8. ESI-MS+ m/z Calcd. for C17H10F6S2O2: 425.0105
[M+H]+, found 425.0118.
Scheme S1: Synthetic scheme for DTE-dialdehyde.
(b) Synthesis of benzene-1,3,5-tricarbohydrazide:
We have synthesized benzene-1,3,5-tricarbohydrazide (compound 6) by adapting reported
procedure.5 The characterization data is found to be similar to the reported one.5b1H NMR (400
MHz, DMSO-D6): 3.32 (s, 6H, -NH2), 8.32 (s, 3H, ArH), 8.49 (s, 3H, -CONH-). 13C NMR (100
Table S3: PL lifetime details
Sample A1(%)
τ
1(ns) A2(%)τ
2 (ns)τ
avg (ns)gfp-I 99.2 0.110 0.08 1.143 0.128
pcCMP-O-gfp-I 99.1 0.113 0.09 1.172 0.123
pcCMP-C-gfp-I 87.4 0.012 12.6 0.063 0.034
8
MHz, CDCl3): 132.6, 136.8, 167.1. ESI-MS+ m/z Calcd. for C9H12N6O3: 253.1049 [M+H]+, found
253.1045.
Scheme S2: Synthetic scheme for benzene-1,3,5-tricarbohydrazide.
(c) Synthesis of gfp chromophore analogue (gfp-I)
:Synthesis of analogue of gfp chromophore: Iodo-labelled gfp chromophore analogue namely,
((Z)-4-(2-hydroxy-3,5-diiodobenzylidene)-1-(4-iodophenyl)-2-methyl-1H-imidazol-5(4H)-one
(gfp-I)) was synthesized and reported previously by us.6 Here, we have employed similar
procedure. Characterization data was matched with the reported one. Synthetic scheme and
characterization data for gfp-I are given below;
The yield of column purified gfp-I is 45%. Rf: 0.5 (35% ethyl acetate: hexane). IR (KBr) νmax/cm
-1 = 3385, 3048, 2919, 2850, 1721, 1637, 1572, 1487, 1403, 1286, 1147, 1008, 944, 759, 737. 1H
NMR (CDCl3, 400 MHz): δ 2.32 (s, 3H, -CH3), 7.01 (d, J= 8.8, 2ArH), 7.04 (s, 1H, =CH), 7.59 (s,
1H, -ArH), 7.87 (d, J= 8.4, 2ArH), 8.11 (s, 1H, -ArH).13C NMR (CDCl3, 150 MHz): 29.6, 80.5,
90.2, 95.1, 121.4, 128.7, 128.9, 132.0, 132.9, 139.1, 144.5, 150.4, 157.0, 157.8, 166.3. ESI-MS+
m/z Calcd. for C17H12I3N2O2: 656.8027 [M+H]+, found 656.8016.
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Encapsulation of gfp-I in the pcCMP-O (pcCMP-O-gfp-I):
The pcCMP-O was activated at 120 °C for 12 hrsprior to encapsulation of the gfp chromophore
analogue (gfp-I). Next, 10 mg gfp-I was dissolved in 15 mL acetonitrile solution followed by addition of 10 mg pcCMP-O into it. The resulting reaction mixture was stirred at room temperature
for 24 hrs and gfp-I encapsulated pcCMP-O (pcCMP-O-gfp-I) was isolated upon centrifugation
and washed with acetonitrile thrice in order to remove excess gfp-I. Presence of gfp-I in
pcCMP-O matrix (pcCMP-pcCMP-O-gfp-I) was confirmed by TGA, EDAX, elemental mapping and CO2
adsorption studies. TGA of pcCMP-O-gfp-I displayed approximately 13% weight loss in the
temperature range of 200 – 250 °C, which could be corresponds to the encapsulated gfp-I
chromophore. EDAX analysis showed presence of iodine and thus corroborates encapsulation of
gfp-I chromophore in the polymer matrix. Calculated amount of gfp-I chromophore in the
pcCMP-O using EDAX analysis was found to be approximately 13% by weight. Elemental mapping as
well as line EDAX revealed that the iodo substituted gfp-I chromophore is distributed in the
polymer matrix. Significant decrease in CO2 sorption at 195 K for pcCMP-O-gfp-I in comparison
to bare pcCMP-O is indicative for the presence of gfp-I inside the pores of polymer. We have
further quantified the amount of encapsulated gfp-I in the pcCMP-O by studying the UV-Vis
absorption studies on mother-liquor before and after encapsulation. The solution of acetonitrile
which contained gfp-I after encapsulation inside pcCMP-O, showed a decrease in absorption
intensity of around 13%. Thus, TGA, UV-Vis and EDAX analyses indicate for the presence of
approximately 13% gfp-I in the matrix of pcCMP-O.
DFT Study
Quantum mechanical calculations were carried out using density functional theory (DFT) and
10
photophysical properties and photo-modulated conductivity associated with pcCMP-O and
pcCMP-C. All computations were performed using Gaussian 09 package.7 Two model systems,
pcCMP-O and pcCMP-C, were considered in computations for the repeating unit of pcCMP-O
and pcCMP-C, respectively (Figure S1). The ground state, transition state and excited state
computations were performed utilizing hybrid density functional method B3LYP in conjunction
with 6-31G* basis set.8 As the B3LYP method provides appreciably accurate geometry but
over-estimates the HOMO-LUMO gap, we utilized HSEH1PBE/6-31+G* method to evaluate molecular
orbital energies.9,10 In all computations, Grimme’s d3 dispersion was also used to tackle weak
interactions.11 Free energy values are reported in k.cal mol-1 at 25 °C.
Figure S1: Structure of the two models, pcCMP-O and pcCMP-C.
Figure S2: (a) D3-B3LYP/6-31G* computed free energies (kcal/mol) for the pcCMP-O ↔
pcCMP-C transformation and (b) D3-HSEH1PBE/6-31+G* calculated HOMO-LUMO gap for
11
The computations revealed that the repeating unit of open form, pcCMP-O is stabilized over
pcCMP-C by 14.6 kcal/mol (Figure S2a). The free energy barrier of transformations, pcCMP-O
→ pcCMP-C and pcCMP-C → pcCMP-O were found to be 30.6 and 16.0 kcal/mol, respectively.
Under this energetic scenario, pcCMP-C cannot be populated significantly from pcCMP-O by
applying heat. Light irradiation is required for this transformation. However, pcCMP-C can be
converted to pcCMP-O by applying little heat or long-standing at 25 °C as the computed barrier
is only 16.0 kcal/mol.
Figure S3. HOMO and LUMO diagrams of model-pcCMP-O and model-pcCMP-C.
The molecular orbital energy analysis of the optimized model systems at
D3-HSEH1PBE/6-31+G* level indicated that pcCMP-O has HOMO-LUMO gap of 3.42 eV (
Figure S2, S3). While in pcCMP-C, the gap was observed to be 1.65 eV which is lower than
12
when compared with pcCMP-O. Considering pcCMP-C and pcCMP-O as intrinsic
semiconductors with same pre-exponential factor, the conductivity relationship with bandgap
becomes σo/σc = e-Eg/KT (where σo = conductivity in open form, σc = conductivity in closed
form, Eg = difference in bandgap, K = Boltzmann constant and T = temperature in Kelvin).
With the difference in HOMO-LUMO gap of 1.77 eV, the conductivity enhancement should
be 187 times i.e. the electrical conductivity of pcCMP-C should be 187 times higher than that
of pcCMP-O. The computational prediction of conductivity enhancement is in good
agreement with the experimentally observed conductivity enhancement by 92 times.
TD-DFT computations were also performed on the repeating unit of pcCMP-O and
pcCMP-C in order to get more insight about the electronic transition. In detail, pcCMP-O revealed the
lowest vertical electronic excitation (LVEE) from HOMO to LUMO at 371 nm (f = 0.03) with
very low intensity and the most intense electronic transition appeared at 361 nm which
associates with HOMO to LUMO+2 transition (f = 1.35) (
Figure S4). In pcCMP-C, the LVEE observed at 708 nm (HOMO→LUMO, f = 0.62) with
moderate intensity (Figure S5). pcCMP-C showed most intense electronic transition at 380
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Figure S4. Computed electronic transitions in pcCMP-O.
Figure S5.Computed electronic transitions in pcCMP-C.
Coordinates: pcCMP-O C 3.506600 1.013800 -0.522000 C 2.867800 2.159500 -0.119500 S 2.423400 -0.013100 -1.439900 C 1.493700 2.219600 -0.520600 H 3.348300 2.940300 0.458600 C 1.108800 1.114200 -1.262600 C 0.643900 3.358100 -0.181300 C -0.213700 0.822800 -1.903300 C -0.652100 3.400900 0.220600 C 1.238300 4.745200 -0.209700 H -0.852500 0.218100 -1.248100 H -0.747900 1.754500 -2.108800 LUMO+2 HOMO HOMO LUMO 371 nm f = 0.03 361 nm f = 1.35 LUMO+2 HOMO HOMO-2 LUMO 708 nm f = 0.62 380 nm f = 0.68
14 H -0.088000 0.280800 -2.845900 C -1.114100 4.828600 0.395200 C -1.545000 2.297500 0.580900 C 0.014400 5.691500 -0.223000 F 2.051300 4.960300 -1.273800 F 1.986200 4.977300 0.919700 F -1.272000 5.140100 1.712600 F -2.307500 5.081900 -0.219800 C -1.183900 1.233500 1.393200 C -2.905300 2.211700 0.140400 F -0.297900 5.985300 -1.509500 F 0.226900 6.837600 0.452600 S -2.501500 0.113300 1.589500 C 0.121300 0.977500 2.083400 C -3.554300 1.085600 0.582800 H -3.372300 2.956200 -0.492100 H 0.773900 0.333500 1.480900 H 0.653400 1.918700 2.247800 H -0.029800 0.492400 3.052900 C -4.916600 0.704200 0.293100 H -5.492800 1.406400 -0.326400 N -5.413600 -0.394500 0.739700 C -7.253600 -1.914200 0.726200 C -8.707100 -2.036000 0.364400 C -9.601900 -0.959000 0.438400 C -9.173600 -3.295300 -0.021400 C -10.950100 -1.136600 0.110700 H -9.252400 0.017600 0.761200 C -10.507600 -3.471700 -0.402800 H -8.496900 -4.142900 -0.031300 C -11.389400 -2.388900 -0.332000 H -12.439600 -2.493000 -0.584500 O -6.616400 -2.826100 1.215700 N -6.707400 -0.664600 0.438800 H -7.219100 -0.030900 -0.173500 C -11.972600 -0.031000 0.174800 C -10.926700 -4.858500 -0.833800 O -12.946500 -0.016500 -0.558200 O -10.328600 -5.850700 -0.458500 N -11.696300 0.935400 1.125500 H -11.120700 0.644700 1.911500 N -12.610500 1.983600 1.310600 H -13.251200 1.771100 2.074200 H -12.093800 2.828900 1.534900 N -12.022100 -4.876200 -1.673900 H -12.254100 -4.018400 -2.165000 N -12.485300 -6.098200 -2.178300 H -13.501000 -6.100600 -2.151800 H -12.175300 -6.228500 -3.139800 C 4.880000 0.652000 -0.260900 N 5.366900 -0.465500 -0.670400 H 5.473800 1.386800 0.301400 N 6.672600 -0.714200 -0.405300 C 7.218000 -1.972100 -0.656000 H 7.203500 -0.047700 0.153300 C 8.686800 -2.065300 -0.351600 O 6.569400 -2.910900 -1.074400 C 9.566300 -0.985400 -0.513900 C 9.182700 -3.301700 0.070000 C 10.929300 -1.136400 -0.238300 H 9.193000 -0.027500 -0.865000 C 10.534000 -3.449300 0.399500 H 8.516100 -4.153600 0.148200 C 11.400500 -2.363600 0.240400 C 11.936300 -0.026000 -0.396500 C 10.985900 -4.811500 0.873500 H 12.461900 -2.447200 0.450000 O 12.941800 0.028600 0.290400 N 11.607500 0.896000 -1.374200 O 10.381800 -5.824600 0.570100 N 12.117400 -4.782300 1.663800 H 11.001100 0.566500 -2.120700 N 12.500900 1.943700 -1.644000 H 12.363700 -3.901200 2.104100 N 12.615100 -5.976400 2.200900 H 13.110400 1.704400 -2.424900 H 11.965400 2.773600 -1.881400 H 13.628500 -5.972600 2.127000 H 12.351300 -6.064700 3.180900 Model-pcCMP-C C 3.186900 1.370700 -0.304200 C 2.821500 2.692400 -0.330700 S 1.838100 0.225100 -0.265100 C 1.418300 2.905400 -0.322700 H 3.537400 3.506600 -0.298800 C 0.616300 1.616100 -0.572700 C 0.711500 4.060400 -0.157300 C 0.242000 1.584400 -2.076400 C -0.721900 4.056100 -0.023100 C 1.225900 5.467200 -0.123200 H -0.258200 0.650000 -2.337600 H -0.422700 2.419100 -2.320100 H 1.150900 1.676500 -2.676100 C -1.226700 5.464900 -0.055400 C -1.422100 2.898800 0.147900 C 0.011800 6.292100 0.396100
15 F 1.562900 5.920400 -1.369900 F 2.324700 5.632100 0.668100 F -2.304600 5.686900 0.746300 F -1.573000 5.862600 -1.319900 C -0.613400 1.607600 0.367100 C -2.824000 2.681500 0.219100 F -0.000800 7.557400 -0.062900 F 0.044800 6.310300 1.754300 S -1.835600 0.221600 0.039000 C -0.237000 1.550100 1.870400 C -3.186600 1.359900 0.170700 H -3.541000 3.493900 0.260800 H 0.421700 2.385000 2.129000 H -1.146100 1.625000 2.472300 H 0.269500 0.614400 2.113300 C 4.550900 0.908900 -0.276000 N 4.815800 -0.353000 -0.223900 H 5.335400 1.677700 -0.293100 N 6.111300 -0.716800 -0.175200 C 6.477200 -2.065200 -0.268100 H 6.835300 -0.002200 -0.242200 C 7.953900 -2.300800 -0.136600 O 5.675000 -2.957300 -0.450300 C 8.783700 -1.502400 0.663900 C 8.496100 -3.393300 -0.818800 C 10.149900 -1.783400 0.765000 H 8.367400 -0.667000 1.219800 C 9.869500 -3.651800 -0.766100 H 7.850700 -4.044100 -1.398800 C 10.688500 -2.844200 0.028600 C 11.103000 -0.974600 1.607300 C 10.380000 -4.837900 -1.552400 H 11.752800 -3.032700 0.124000 O 12.279700 -0.861200 1.310400 N 10.516900 -0.392400 2.717100 O 9.652900 -5.772300 -1.837600 N 11.712400 -4.747800 -1.901100 H 9.686300 -0.851200 3.082200 N 11.322400 0.344800 3.598200 H 12.143400 -3.828600 -1.890100 N 12.296100 -5.766500 -2.665000 H 10.778500 1.121900 3.961700 H 11.633800 -0.237700 4.374400 H 12.381400 -5.479000 -3.638400 H 13.220300 -5.967500 -2.293600 C -4.549000 0.893400 0.192800 N -4.813800 -0.367000 0.112900 H -5.333500 1.658400 0.270300 N -6.110200 -0.732300 0.113800 C -6.470800 -2.083400 0.179500 H -6.830500 -0.021800 0.238400 C -7.952200 -2.316900 0.112200 O -5.660800 -2.980000 0.293000 C -8.820200 -1.493400 -0.619400 C -8.460600 -3.432000 0.783700 C -10.189900 -1.772400 -0.662200 H -8.431300 -0.639400 -1.166800 C -9.835100 -3.689900 0.790700 H -7.787600 -4.100900 1.309100 C -10.692100 -2.857300 0.064700 C -11.183400 -0.937400 -1.428900 C -10.307000 -4.901700 1.561600 H -11.759900 -3.043700 0.016300 O -12.344500 -0.837500 -1.071500 N -10.652800 -0.315500 -2.545000 O -9.569000 -5.846300 1.775700 N -11.618700 -4.821300 1.983900 H -9.840100 -0.758600 -2.965700 N -11.501700 0.448200 -3.360500 H -12.045800 -3.901300 2.028400 N -12.163900 -5.864600 2.743100 H -10.977600 1.239100 -3.723200 H -11.848800 -0.108900 -4.140200 H -12.192700 -5.611600 3.729300 H -13.108700 -6.048900 2.417600 TS (model-O ↔ model-C): C 3.280600 1.297900 -0.360900 C 2.869400 2.605500 -0.391700 S 1.959600 0.107100 -0.344800 C 1.453100 2.760700 -0.393100 H 3.554800 3.444000 -0.336700 C 0.744300 1.447700 -0.690200 C 0.714200 3.885600 -0.168700 C 0.247200 1.391800 -2.134100 C -0.722600 3.882000 -0.003300 C 1.229500 5.294100 -0.116100 H -0.256600 0.444000 -2.337300 H -0.453800 2.210800 -2.324500 H 1.095400 1.493100 -2.819500 C -1.217900 5.295700 -0.063000 C -1.455800 2.754900 0.222300 C 0.016100 6.122500 0.393200 F 1.587500 5.753100 -1.355000 F 2.319300 5.452200 0.691000 F -2.305400 5.541200 0.718500 F -1.541200 5.675900 -1.339600 C -0.740700 1.435500 0.480000 C -2.872000 2.595600 0.283300 F 0.008600 7.386500 -0.069800 F 0.039200 6.145200 1.751600
16 S -1.957800 0.104200 0.103300 C -0.244900 1.343600 1.922600 C -3.281200 1.288900 0.222300 H -3.559700 3.433100 0.307200 H 0.452100 2.160500 2.135700 H -1.094400 1.423100 2.609300 H 0.262700 0.392800 2.100800 C 4.656200 0.877800 -0.308700 N 4.955500 -0.376800 -0.255900 H 5.419000 1.668200 -0.310500 N 6.259400 -0.704700 -0.187200 C 6.664300 -2.041600 -0.288500 H 6.964500 0.029900 -0.239100 C 8.145000 -2.236300 -0.138900 O 5.890200 -2.953700 -0.491600 C 8.938600 -1.427600 0.687600 C 8.729600 -3.299700 -0.832000 C 10.311000 -1.669400 0.804000 H 8.489100 -0.615100 1.251400 C 10.109400 -3.517400 -0.763900 H 8.112600 -3.959300 -1.432600 C 10.892000 -2.699800 0.057000 C 11.227300 -0.847400 1.674200 C 10.667100 -4.672700 -1.564000 H 11.960100 -2.857600 0.164600 O 12.404100 -0.693500 1.396500 N 10.608300 -0.302800 2.785100 O 9.973100 -5.623200 -1.876900 N 12.000900 -4.535500 -1.891400 H 9.786400 -0.792100 3.129900 N 11.378400 0.442800 3.690400 H 12.403700 -3.604300 -1.855700 N 12.626600 -5.521200 -2.665000 H 10.806300 1.196900 4.058800 H 11.696100 -0.143400 4.461200 H 12.719100 -5.212000 -3.631100 H 13.550300 -5.702700 -2.282300 C -4.656700 0.865300 0.221400 N -4.956300 -0.386800 0.128500 H -5.420000 1.651800 0.295900 N -6.262000 -0.715800 0.114100 C -6.659200 -2.057300 0.169700 H -6.963500 0.012900 0.241600 C -8.146100 -2.250600 0.099500 O -5.873600 -2.975900 0.278900 C -8.991700 -1.399700 -0.627000 C -8.684300 -3.355500 0.764700 C -10.368500 -1.641400 -0.670600 H -8.580300 -0.553300 -1.169800 C -10.065300 -3.576200 0.771000 H -8.029500 -4.045300 1.286000 C -10.899700 -2.716400 0.050400 C -11.339500 -0.775600 -1.432000 C -10.569500 -4.779000 1.535300 H -11.972200 -2.873400 0.001800 O -12.497000 -0.645600 -1.072800 N -10.793100 -0.163000 -2.545700 O -9.857500 -5.744800 1.743100 N -11.878000 -4.665100 1.959600 H -9.992900 -0.625900 -2.969000 N -11.621500 0.627200 -3.356900 H -12.279500 -3.733900 2.010200 N -12.450800 -5.697300 2.713500 H -11.076600 1.405500 -3.716100 H -11.983800 0.083400 -4.139000 H -12.470500 -5.449900 3.701400 H -13.401100 -5.853000 2.389000
17
Characterization data:
Figure S6: TGA plot for pcCMP-O, recorded in N2 atmosphere.
Figure S7: Methanol solvents adsorption at 293 K for pcCMP-O.
0.0
0.2
0.4
0.6
0.8
1.0
0
50
100
150
200
250
Solv
en
t ads
or
ptio
n (mL
/g)
Relative Pressure (P/P0)
Methanol_ads. Methanol_des.0
100 200 300 400 500 600 700 800
40
50
60
70
80
90
100
Wei
gh
t (%)
Temperature (
C)
313
C
18
Figure S8: A comparison of UV-Vis spectra for pcCMP-C before and after heating at the
135 C, indicating formation of pcCMP-O upon heating.
Figure S9: FE-SEM image (left) and TEM image (right) for pcCMP-C.
Figure S10: CV experiment for pcCMP-O in 0.1M TBAF acetonitrile solution.
300 400 500 600 700 0.2 0.4 0.6 0.8 1.0 heating at 135 C pcCMP-C_after heating pcCMP-O pcCMP-C
Normallized absorbance (O.
D.) Wavelength (nm) -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 j (mA/cm 2 ) Potential (V) vs Ag/AgNO3 pcCMP-O
19
200
400
600
800
20
40
60
80
100
We
igh
t (%)
Temperature (
C)
13% weigth lossFigure S11: TGA plot for gfp -I chromophore encapsulated in pcCMP-O (pcCMP-O-gfp
-I), recorded under N2 atmosphere.
Figure S12: UV-Vis spectra of gfp-I solution (10-5 M) in acetonitrile; before and after encapsulation of gfp-I in the pcCMP-O.
20
Figure S13: CO2 gas adsorption at 195 K before and after gfp chromophore encapsulation
in pcCMP-O.
Figure S14: Elemental mapping for pcCMP-O-gfp-I. Scale bar is correspond to 5 µM.
Figure S15: FE-SEM image (above) and EDX analysis for pcCMP-O-gfp-I.
0.0 0.2 0.4 0.6 0.8 1.0
0
20
40
60
80
After doping Before doping adsorption desorptionU
ptak
e
(c
c
/g)
Relative Pressure (P/P
0)
adsorption desorption pcCMP-O21
Elemental analysis from EDX data:
% calculation of gfp-I in pcCMP matrices:
a) Theoretical elemental analysis:
Per unit molecular weight for pcCMP = 852 and the atomic % is expected to be C = 48.59%;
F = 20.05%; N = 9.85%; O = 7.50%; S = 11.28%.
The molecular weight for gfp-I = 656 and atomic % for C = 31.13%; I = 58.04%; N =
4.27%; O = 4.88%.
Now, if the equal weight ratio (1:1) of both, pcCMP and gfp-I is present in polymer matrices
then the molar ration of pcCMP and gfp-I will be assigned to 1:0.77 (as per their molecular
weight). And as the results, the theoretical % of iodine in polymer matrices is expected to
be 19.4% (when weight ratio of pcCMP and gfp-I is equal).
b) However, the obtained iodine % in polymer matrices by EDX analysis was found to be
2.47%.
Therefore, the percentage of iodine which also represents the % gfp-I in polymer is found
to be = 2.47x100/19.4 = 12.7%.
Elements
Wt%
Carbon 60.40 Nitrogen 3.23 Oxygen 20.21 Fluorine 10.68 Sulphur 3.01 Iodine 2.47 Total 10022
Figure S16: IR spectrum for pcCMP-O.
Figure S17: Combined IR plot for pcCMP-O (pink) and pcCMP-O-gfp-I (blue) for
comparison. 4000 3500 3000 2500 2000 1500 1000 500 1444 cm-1 (Ar(-C=C-)) 1267 cm-1(-C-F) 733 cm-1 (-C-F) 3213 cm-1 (-N-H) 1671 cm-1 (-C-N-)
Wavenumber (cm
-1)
IR data_pcCMP-O
1608 cm-1 (-C=N-)4000 3500 3000 2500 2000 1500 1000
500
1724 cm-1(-
C=O
)
Wavenumber (cm-1)
pcCMP
pcCMP-
gfp-I
3435 cm-1(-
O-H
)
23
Figure S18: Excited-state lifetime plot upon excitation at 370 nm for pcCMP-O-gfp-Iand
pcCMP-C-gfp-I and bare gfp-I.
Time dependent UV-Vis absorption spectra:
Figure S19: Time-dependent UV-Vis absorption spectra for (a) Visible-light irradiation (pcCMP-C to pcCMP-O); (b) linear fit for absorbance changes at 632 nm for close→open; (c) UV-light irradiation (pcCMP-O to pcCMP-C); (d) linear fit for absorbance changes at 632 nm for open→close.
prompt pcCMP-C-gfp-I pcCMP-O-gfp-I gfp-I fitting fitting fitting 5 10 15 0.001 0.01 0.1 1 Counts Times (ns) 0 200 400 600 800 1000 1200 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 Absorbance at 632 nm Time (seconds) (a) (b) 300 400 500 600 700 800 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Absorbance (O.D.) Wavelength (nm) Close form 0.5 min_Vis 1 min_Vis 2.5 min_Vis 5 min_Vis 7.5 min_Vis 10 min_Vis 15 min_Vis 20 min_Vis Visible Light Irradiation 300 400 500 600 700 800 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Absorbance (O. D.) Wavelength (nm) Open form 30 sec._UV 60 sec._UV 90 sec_UV 120 sec_UV 150 sec_UV 180 sec_UV UV-light Irradiation (c) (d)
24
Absorption Coefficient for pcCMP-O and pcCMP-C:
Figure S20: Absorption coefficient calculated from the UV-Vis spectra recorded by
making thin film for (a) pcCMP-O and (b) pcCMP-C. Film thickness was 975 nm in both cases. 300 400 500 600 700 800 0 1000 2000 3000 4000 5000 6000 7000 Absoprtion Coefficient Wavelength (nm) pcCMP-O
(a)
300 400 500 600 700 800 1000 2000 3000 4000 5000 6000 7000 8000 Absorption Coefficient Wavelength (nm) pcCMP-C(b)
25
1
H and
13C-NMR Spectra:
Figure S21: (a) 1H-NMR (400 MHz) and (b) 13C-NMR (100 MHz) for DTE-dialdehyde,
recorded in CDCl3 solvent.
(a)
26
Figure S22: (a) 1H-NMR (400 MHz) and (b) 13C-NMR (100 MHz) for
benzene-1,3,5-tricarbohydrazide, recorded in DMSO-D6 solvent.
(a)
27
Figure S23: (a) 1H-NMR (400 MHz) and (b) 13C-NMR (150 MHz) for gfp-I, recorded in
CDCl3 solvent.
(a)
28
References:
1. A. Vogel, Vogel’s textbook of practical organic chemistry (eds), B S Furniss, A J Hannaford, P W G Smith and A R Tatchell, ELBS Longman Singapore Publishers Pvt. Ltd, Singapore, 5th edn, 1996, Chapter 8th, 1155.
2. Z. Zhang, W. Wang, P. Jin, J. Xue, L. Sun, J. Huang, J. Zhang, H. Tian, Nat. Commun.
2019,10, 4232.
3. D. E. Williams, J. A. Rietman, J. M. Maier, R. Tan, A. B. Greytak, M. D. Smith, J. A. Krause and N. B. Shustova, J. Am. Chem. Soc.2014, 136, 11886.
4. D. Samanta, A. Singh, P. Verma, S. Bhattacharyya, S. Roy, T. K. Maji, J. Org. Chem.,
2019, 84, 10946.
5. (a). C. He, Z. Lin, Z. He, C. Duan, C. Xu, Z. Wang, C. Yan, Angew. Chem. Int. Ed.
2008, 47, 877; (b). K. P. Rakesh, C. S. Shantharam, D. M. S. Vardhan, N. M. M. Gowda, M. B. Sridhara, D. C. Gowda, EPJMR, 2016, 3(3), 362.
6. A. Singh, D. Samanta, M. Boro, T. K. Maji, Chem. Commun. 2019, 55, 2837.
7. Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT,
2009.
8. A.D. Becke, J. Chem. Phys.1993, 98, 5648.
9. A. V. Krukau, O. A. Vydrov, A. F. Izmaylov, and G. E. Scuseria, J. Chem. Phys.,2006,
125, 224106.
10.M. Rajeshirke, M. C. Sreenath, S. Chitrambalam, I. H. Joe, N. Sekar, J. Phys. Chem. C,2018, 122,14313.
