Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2018.

Supporting Information
for Adv. Funct. Mater., DOI: 10.1002/adfm.201800342

A Simple and Versatile Pathway for the Synthesis of Visible

Light Photoreactive Nanoparticles
Laura Delafresnaye, Neomy Zaquen, Rhiannon P. Kuchel,
James P. Blinco, Per B. Zetterlund,* and Christopher Barner-
Kowollik*
Supporting Information
A Simple and Versatile Pathway for the Synthesis of Visible Light
Photoreactive Nanoparticles

Laura Delafresnaye, Neomy Zaquen, Rhiannon P. Kuchel, James P. Blinco, Per B. Zetterlund*
and Christopher Barner-Kowollik*

1. Experimental Section

1.1. Materials

All materials were reagent grade and used as received, unless stated otherwise. Hexadecane

(HD, 99% Sigma Aldrich) and 1,2-dichloroethane (98 % Sigma Aldrich) were used as co-

solvent. Sodium dodecyl sulfate (SDS; Technical Grade, Ajax Chemicals) was used as anionic

surfactant. Deionized (DI) water was produced by a Milli-Q reverse osmosis system and had a

resistivity of > 18 mΩ·cm-1. Methyl methacrylate (MMA; > 99 %, Sigma Aldrich) was

deinhibited by passing through a column of activated basic alumina (Ajax). The deinhibited

monomer was stored in the freezer at -20°C and used within 1 month. Azobisisobutyronitrile

(AIBN, 97%, VWR) was recrystallized twice from methanol.

1.2. Characterization

Gravimetric measurements: Monomer conversions were obtained by gravimetric

measurements. After completion of the polymerization, a 2 mL aliquot was transferred to a

weighted aluminium tray and reweighted. After drying 2 nights in a vacuum oven at 40 °C, the

tray was reweighted and the conversion of monomer was calculated from the difference in

weight based on the miniemulsion recipe.

Nuclear Magnetic Resonance (NMR) Spectrometry: NMR spectra of the copolymers were

obtained using a Bruker Avance 400 spectrometer (400 MHz). NMR spectra of the monomers

as well as the copolymers after NITEC/NICAL reactions were obtained using a Bruker Avance

600 spectrometer (600 MHz). All chemical shifts are recorded in ppm (δ) relative to

tetramethylsilane (δ = 0 ppm), referenced to the chemical shifts of residual solvent resonances

(1H). 19F NMR spectra were recorded without proton decoupling using 12 s delay and 128 scans.

The multiplicities were explained using the following abbreviations: s for singlet, d for doublet,

t for triplet, m for multiplet and bs for broad signal. The dried samples obtained for gravimetric

analysis were redissolved in deuterated solvent and used for NMR measurements.

Fourier Transform Attenuated Total Reflectance (FT-ATR) Spectroscopy: All measurements

were performed on a Bruker IFS 66/S Fourier transform spectrometer equipped with a tungsten

halogen lamp, a CaF2 beam splitter. Spectra were analyzed with OPUS software. The dried

samples obtained for gravimetric analysis were redissolved in deuterated solvent and used for

FT-ATR measurements.

Size Exclusion Chromatography (SEC) THF: The molecular weight and polydispersity of

synthesized polymers were analyzed via size exclusion chromatography (SEC). A Shimadzu

modular system containing a DGU-12A degasser, a LC-10AT pump, a SIL-10AD automatic

injector, a CTO-10A column oven and a RID-10A refractive index detector were used. A 50 x

7.8 mm guard column and four 300 x 7.8 mm linear columns (500, 103, 104, 105 Å pore size,

5 μm particle size) were used for analyses. Tetrahydrofuran (THF, HPLC Grade) with a flow

rate of 1 mL min-1 was used as the mobile phase. The injection volume was 50 μL. The samples

were prepared by dissolving 2-3 mg mL-1 of the analyte in tetrahydrofuran, followed by

filtration through a 0.45 μm filter. The unit was calibrated using commercially available linear

PMMA standards (0.5-1000 kDa, Polymer Laboratories). Chromatograms were processed

using Cirrus 2.0 software (Polymer Laboratories).

2
Dynamic Light Scattering (DLS): Particle sizes (the average diameters and size distributions)

were determined using a Malvern Zetaplus particle size analyzer (laser, 35mW, λ = 632 nm,

angle = 90 °). Samples (1 droplet of latex; approx. 250 mg) were prepared in Milli-Q water for

DLS analysis. The count rate was kept in between 100 and 500 kcps, thereby highly diluting

the latex samples, leading to almost translucent solutions.

Ultraviolet Visible Spectroscopy (UV-Vis): UV-Vis spectra were recorded on a Varian Cary

300 UV-Vis-NIR spectrophotometer (scan rate 600 nm min-1, continuous run from 200 to 800

nm) equipped with a temperature controller. 1 Droplet of latex (250 mg) was prepared in Milli-

Q water for UV Analysis. UV-Vis spectra of the latexes after irradiation were recorded on a

Shimadzu UV-2700 spectrophotometer equipped with a CPS-100 electronic temperature

control cell positioner. A 50 μL droplet was diluted with a factor of 250 using Milli-Q water.

Fluorescence Intensity: The fluorescence intensities of the latexes were measured using a Cary

Eclipse Fluorescence Spectrophotometer (Agilent Technologies). The excitation wavelengths

were 293 nm and 348 nm for the latexes prepared with the UV and Visible light monomers,

respectively. 1 Droplet of latex (250 mg) was prepared in Milli-Q water for UV Analysis and

diluted with a factor of 1000 for fluorescence measurements. After irradiation, the excitation

wavelengths used were 390 nm and 350 nm for the latexes prepared with the UV and Visible

light monomers, respectively. A 10 μL droplet was diluted with a factor of 250 using Milli-Q

water.

Centrifuge: The latexes were purified using a Hettich Universal 320 centrifuge set up with a

Hettich fixed angle rotor 24 x 2 mL place. The sample was centrifuged at 14 500 rpm for 5 min

and the precipitate was washed and then redispersed with Milli-Q water. This procedure was

performed twice.

Transmission Electron Microscopy (TEM): A FEI Tecnai G2 20 TEM operating at 200 kV was

used to characterise the morphology and shape of the nanoparticles. Samples were prepared by

diluting the final latexes in water. 1 drop of the diluted latex was deposited on a Formvar coated
3
copper grid and left to dry for 1 minute. The samples were then stained for 1 h using a vapour

of osmium tetroxide (OsO4) at 2 wt %. Staining was used to improve the visibility of the particle

on the grid.

Scanning Electron Microsopy (SEM): A FEI NOVA NanoSEM 230 SEM at 5 kV and a spot

size of 3 was used to characterise the morphology and shape of the nanoparticles. Samples were

prepared by depositing the dried latex powder onto double sided carbon tape. The samples were

then coated with a 5 nm platinum coating under an angle of 45 °. The coating was used to

improve the visibility of the particles on the SEM holder.

Electrospray Ionization Mass Spectrometry (ESI-MS): Samples were run on an Orbitrap LTQ

XL ion trap mass spectrometer using a nanospray (nanoelectrospray) ionization source to

generate ions from the analyte in solution. The instrument was calibrated with a standard

calibration solution (as outlined in the instrument manual) on the day of analysis using direct

infusion into the ESI source. The instrument conditions were optimized for sensitivity of the

compounds using LC tune software. The analysis was carried out in positive ion mode using

the orbitrap FTMS analyser at a resolution of 60 000. Samples, at a concentration of ca. 1 μg

mL-1 in THF / methanol (3/2 v/v%), were injected into a glass needle and inserted into the

nanospray source. Ions generated were measured over the mass range 150 to 2000 Da window.

Data was acquired in full scan mode over 30 seconds. Data was analysed using the Qual

Browser feature in Xcalibur 2.1.

X-ray Photoelectron Spectroscopy (XPS): XPS samples were prepared by drying the liquid

latex in a vacuum oven at 40 °C for 2 nights, immediately after sampling from the reactor vessel.

The powder-like material was subsequently casted on Indium foil for XPS analysis. X-Ray

Photoelectron Spectroscopy analysis was performed under incident conditions, the X-ray

penetration depth being lower than 5 nm (ultrathin layer method). A Kratos Axis ULTRA XPS

incorporating a 165 mm hemi-spherical electron energy analyzer was used. The incident

radiation was monochromatic A1 X-rays (1486.6 eV) at 225W (15 kV, 15 mA). Survey (wide)
4
scans were taken at analysing pass energy of 160 eV and multiplex (narrow) higher resolution

scans at 20 eV. Survey scans were carried out over 1360-0 eV binding energy range with 1.0

eV steps and a dwell time of 100 ms. Narrow higher resolution scans were run with 0.2 eV steps

and 250 ms dwell time. Base pressure in the analysis chamber was 1.0 109 Torr and during

sample analysis 1.0 108 Torr. The experimental data were analysed using the software Avantage.

Atomic percentage calculations

The theoretical atomic percentage were calculated from the mole number of each reactant.

Water and AIBN were excluded from the calculation. Hydrogen atoms were also excluded

from calculation since it is not detected by XPS. Nitrogen and bromine atomic percentage

were calculated as follows:

𝑥𝑇
𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝐴𝑡𝑜𝑚𝑖𝑐 % = 𝑎 𝑀𝑀𝐴+𝑏 𝑇 +𝑐𝑧 𝑆𝐷𝑆+𝑑 𝐵𝑟 × 100 Equation S1
𝑧

𝑦 𝐵𝑟
𝐵𝑟𝑜𝑚𝑖𝑛𝑒 𝐴𝑡𝑜𝑚𝑖𝑐 % = 𝑎 𝑀𝑀𝐴+𝑏 𝑇 +𝑐 𝑆𝐷𝑆+𝑑 𝐵𝑟 × 100 Equation S2
𝑧

Where x and y are the number of nitrogen and bromine and a, b, c and d refer to the number

of heavy atoms (i.e. detected by XPS) in MMA, Tz monomer, SDS and the Br-reactant (BPM

or BVA), respectively. For clarification, those values are reported in the table below.

PMMA- PMMA- PMMA-Tz- PMMA-Tz- PMMA-Tz- PMMA-Tz-

Value
Tz-UV Tz-Vis UV-BPM UV-BVA Vis-BPM Vis-BVA
x 4 4 3 2 3 2
y 0 0 1 1 1 1
a 7 7 7 7 7 7
b 38 46 38 38 46 46
c 17 17 17 / 0 a 17 / 0 a 17 / 0 a 17 / 0 a
d 0 0 14 8 14 8
a
When the nanoparticles are washed, no SDS is present on the surface so the SDS content is
removed from calculation.

5
The experimental mole percentage of nitrogen at the nanoparticles surface after polymerization

was calculated using the experimental XPS results. 3 equations with 3 unknowns were

established and solved with the software Wolfram Mathematica:

X = Tz mole fraction at the surface

Y = SDS mole fraction at the surface
Z = MMA mole fraction at the surface

𝑋+𝑌+𝑍 =1
𝑌
𝑆(𝐴%) =
7 𝑍 + 38 or 46 𝑋 + 17 𝑌
4𝑋
𝑁(𝐴%) =
7 𝑍 + 38 or 46 𝑋 + 17 𝑌

1.3. Synthesis of UV light tetrazole monomer

Synthesis of 11-hydroxyundecyl (E)-4-((2-tosylhydrazineylidene)methyl)benzoate

Scheme S1. Reaction scheme for the synthesis of 11-hydroxyundecyl 4-formylbenzoate

4.60 g formylbenzoic acid (30.6 mmol, 1.0 eq.), 5.14 g sodium hydrogen carbonate (61.2 mmol,

2.0 eq.) and 10.0 g 11-bromoundecan-1-ol (39.8 mmol, 1.3 eq.) were dissolved in 40 mL of

DMF. The mixture was heated to 125 °C for 2 h and then cooled down to ambient temperature.

The salt was filtered out and 200 mL ethyl acetate were added. The crude reaction mixture was

then washed 3 times with brine (40 mL) and the organic layer was dried over magnesium

sulphate. The solvent was evaporated under reduced pressure and the obtained white paste was

used without further purification (8.80 g, yield 89.7%).

6
Scheme S2. Reaction scheme for the synthesis of 11-hydroxyundecyl (E)-4-((2-
tosylhydrazineylidene)methyl)benzoate.

Compound (1) (8.80 g, 27.4 mmol, 1.0 eq.) was dissolved in 80 mL ethanol and 5.63 g p-

toluenesulfonylhydrazide (30.2 mmol, 1.1 eq.) was added to the solution and stirred overnight.

Subsequently, ethanol was evaporated under reduced pressure and the obtained white paste was

dried under high vacuum. 1H NMR (600 MHz , DMSO-d6) δ [ppm] = 11.71 (s, 1 H), 8.30 (s, 1

H), 7.97 – 7.94 (m, 2 H), 7.78 – 7.76 (m, 2 H), 7.71 – 7.68 (m, 2 H), 7.43 – 7.40 (m, 2 H), 4.38

– 4.32 (m, 2 H), 4.27 – 4.25 (m, 2 H), 3.47 – 3.44 (m, 2 H), 2.36 (s, 3H), 1.72 – 1.67 (m, 2 H),

1.41 – 1.35 (m, 2 H), 1.32 -1.24 (m, 14 H); 13C NMR (151 MHz , DMSO-d6) δ [ppm] = 165.7,

145.9, 144.0, 138.45, 136.5, 130.2, 129.9, 128.1, 127.7, 65.3, 61.2, 56.5, 33.3, 29.6, 29.4, 29.1,

28.6, 25.9, 21.5 (Figure S1 and Figure S2).

r s
b d f h j l m q
a H2O
n
c e g i k r
m o q
n
p

DMSO

d, e, f, g, h, i, j

m
nq l
r
b c
a k
p o

12 11 10 9 8 7 6 5 4 3 2 1 0

/ ppm

Figure S1. 1H NMR spectrum (600 MHz, 256 scans, DMSO-d6) of 11-hydroxyundecyl (E)-4-((2-
tosylhydrazineylidene)methyl) benzoate (2) : δ 11.69 (s, 1H), 8.01 – 7.90 (m, 2H), 7.82 – 7.75 (m, 1H), 7.69 (dd,
J = 8.4, 1.8 Hz, 2H), 7.41 (dd, J = 8.1, 6.2 Hz, 2H), 4.43 – 4.20 (m, 3H), 3.44 (dt, J = 10.6, 5.3 Hz, 1H), 3.37 (dd,

7
J = 7.2, 3.2 Hz, 8H), 2.38 (d, J = 18.8 Hz, 3H), 1.69 (q, J = 6.9 Hz, 1H), 1.38 (h, J = 7.3, 6.8 Hz, 3H), 1.34 – 1.19
(m, 9H), 1.06 (t, J = 7.0 Hz, 2H).

c e g k t u
a i
m n o s
v
l
b d f h j r t
n s
o p q
DMSO

a d-h
n, o ,s ,t
b, j u
* c, i

q m k
l rpv

200 180 160 140 120 100 80 60 40 20 0

/ ppm
Figure S2. 13C NMR spectrum (600 MHz, 1024 scans, DMSO-d6) of 11-hydroxyundecyl (E)-4-((2-
tosylhydrazineylidene)methyl)benzoate (2).

Synthesis of 11-hydroxyundecyl 4-(2-(4-methoxyphenyl)-2H-tetrazol-5-yl)benzoate (Tz-UV

precursor)

Scheme S3. Reaction scheme for the synthesis of 11-hydroxyundecyl 4-(2-(4-methoxyphenyl)2H-tetrazol-5-

yl)benzoate).

2.0 g p-anisidine (16.3 mmol, 1.0 equiv.) was dissolved in 40 mL of a solvent mixture of

HCl/water/ethanol (1:3:3). Subsequently, 1.12 g sodium nitrite (16.3 mmol, 1.00 equiv.) was

dissolved in a second round bottom flask in 7 mL of solvent mixture of ethanol and water (1:1).

The solutions were slowly combined and stirred for 10 minutes at 0 °C. 8.0 g of compound (2)

(16.4 mmol, 1.0 equiv.) was dissolved in 80 mL of pyridine and cooled to -10 °C. The prepared

8
diazonium salt was then slowly added. After complete addition, the solution was stirred at 0 °C

for 1 h and 3 h at ambient temperature. The red solution was precipitated into 1 L of a 1 M

hydrochloric solution. The raw product was recrystallized three times from a mixture

cyclohexane/ethyl acetate (10/1). After drying under high vacuum, compound (3) was obtained

as a pink solid (2.81 g, yield 37 %). 1H NMR (600 MHz , DMSO-d6) δ [ppm] = 8.27-8.26 (d, 2

H), 8.13-8.12 (d, 2 H), 8.07 – 8.05 (d, 2 H), 7.22 – 7.19 (d, 2 H), 4.34 – 4.32 (t, 1 H), 4.29 –

4.27 (t, 2 H), 3.86 (s, 3H), 3.36 – 3.38 (m, 2H), 1.73 – 1.68 (m, 2 H), 1.41 – 1.36 (m, 4 H), 1.33

-1.32 (m, 2 H), 1.27 - 1.23 (m, 10 H); 13C NMR (151 MHz , DMSO-d6) δ [ppm] = 165.6,163.8,

160.9, 132.0, 131.1, 130.5, 129.9, 127.3, 122.1, 115.6, 65.5, 61.2, 56.2, 33.0, 29.57, 29.5, 29.5,

29.4, 29.2, 28.6, 26.0, 25.9 (Figure S3 and Figure S4).

q H2O
b d f h j l m
a n
o p q
c e g i k
m
n
o p

e, f, g, h, i

m n p DMSO
o a b
l
d, j
k c

9 8 7 6 5 4 3 2 1 0

/ ppm

Figure S3. 1H NMR spectrum (600 MHz, 256 scans, DMSO-d6) of 11-hydroxyundecyl 4-(2-(4-methoxyphenyl)-
2H-tetrazol-5-yl)benzoate (Tz-UV precursor, 3): δ 8.29 – 8.24 (m, 1H), 8.15 – 8.10 (m, 1H), 8.09 – 8.03 (m, 1H),
7.24 – 7.18 (m, 1H), 4.35 – 4.25 (m, 2H), 3.86 (s, 2H), 3.39 – 3.32 (m, 1H), 1.71 (p, J = 6.8 Hz, 1H), 1.43 – 1.34
(m, 3H), 1.31 (s, 1H), 1.27 – 1.21 (m, 6H).

9
 a c e g i k
mn o
d h j
l
q s t v
b f n u
p
o r
s t

t
o
a d, e, f, g, h
v
sn b j c

k
lqu pr
m

200 180 160 140 120 100 80 60 40 20 0

/ ppm
Figure S4. 13C NMR spectrum (600 MHz, 1024 scans, DMSO-d6)of 11-hydroxyundecyl 4-(2-(4-
methoxyphenyl)-2H-tetrazol-5-yl)benzoate (Tz-UV precursor, 3).

Synthesis of 11-(acryloyloxy)undecyl 4-(2-(4-methoxyphenyl)-2H-tetrazol-5-yl)benzoate (Tz-

UV monomer)

Scheme S4. General reaction scheme of the synthesis of 11-(acryloyloxy)undecyl 4-(2-(4-methoxyphenyl)-2H-

tetrazol-5-yl)benzoate (Tz-UV monomer).

In a flame dried schlenk flask, 2.81 g (6.03 mmol, 1.0 eq.) compound (3) and 10 mL (71.69

mmol, 11.89 eq.) triethylamine were dissolved in 150 mL of dry THF and subsequently cooled

to 0 °C. 6 mL (73.58 mmol, 12.2 eq.) acryloyl chloride was slowly added under an inert

atmosphere. The reaction was stirred for three hours at 0°C and then over night at ambient

temperature. The salt was filtered out and the solvent was evaporated under reduced pressure.

The crude product was purified by flash chromatography (silica gel, cyclohexane/ethyl acetate,

95/5 v/v) to obtain 1.00 g of a yellowish powder (yield 32 %). 1H NMR (600 MHz , CDCl3) δ

[ppm] = 8.26-8.25 (d, 2 H), 8.13-8.11 (d, 2 H), 8.07 – 8.04 (d, 2 H), 7.02 – 7.00 (d, 2 H), 6.34
10
– 6.31 (d, 1 H), 6.07 - 6.03 (m, 1 H), 5.75 – 5.73 (d, 1H), 4.30 – 4.28 (t, 2 H), 4.09 – 4.07 (t, 2

H), 3.84 (s, 3H), 1.75 – 1.71 (m, 2 H), 1.62 – 1.58 (m, 2 H), 1.42 -1.37 (m, 2 H), 1.30 - 1.23 (m,

12 H); 13C NMR (151 MHz , CDCl3) δ [ppm] = 166.6, 166.1, 160.7, 132.1, 131.3, 130.4, 130.2,

128.7, 126.9, 121.5, 114.8, 65.5, 64.7, 55.7, 29.5, 29.3, 29.3, 28.7, 28.6, 26.1, 25.9; HRMS

[M+Na]+ m/z: calcd for C29H36N4O5, Na+ 543.2592 found 543.2580 (Figure S5 and Figure S6).

a d f h j l n o
b p q r
c e g i k m
o
p
q r s

g-l

H2O

d
op n
q r

b a f
c me

9 8 7 6 5 4 3 2 1 0

/ ppm

Figure S5. 1H NMR spectrum (600 MHz, 256 scans, CDCl3) of 11-(acryloyloxy)undecyl 4-(2-(4-methoxyphenyl)-
2H-tetrazol-5-yl)benzoate (Tz-UV monomer, 4): δ 8.26 (dd, J = 7.8, 1.1 Hz, 3H), 8.15 – 8.09 (m, 4H), 8.10 – 8.02
(m, 4H), 7.19 (s, 3H), 7.03 – 6.98 (m, 3H), 6.32 (ddd, J = 17.3, 1.5, 0.7 Hz, 2H), 6.05 (ddd, J = 17.2, 10.4, 0.7 Hz,
2H), 5.74 (ddd, J = 10.4, 1.5, 0.7 Hz, 2H), 4.29 (t, J = 6.7 Hz, 4H), 4.08 (td, J = 6.8, 0.7 Hz, 4H), 3.84 (d, J = 0.7
Hz, 5H), 1.72 (q, J = 7.1 Hz, 4H), 1.59 (q, J = 7.0 Hz, 4H), 1.49 (s, 11H), 1.39 (q, J = 7.7 Hz, 4H), 1.29 (d, J = 4.7
Hz, 4H), 1.19 (s, 1H), 0.77 (s, 2H).

11
 a d f h j l n p q r
c o v w
b e g i k m s
q u
r t x
v w y

q g -k
w
v r
m
a n y
u e fl
b d
co x ps
t

200 180 160 140 120 100 80 60 40 20 0

/ ppm
Figure S6. 13C NMR spectrum (600 MHz, 1024 scans, CDCl3) of 11-(acryloyloxy)undecyl 4-(2-(4-
methoxyphenyl)-2H-tetrazol-5-yl)benzoate (Tz-UV monomer, 4).

1.4. Synthesis of Visible light tetrazole monomer

Synthesis of 11-hydroxyundecyl 4-(2-(pyren-1-yl)-2H-tetrazol-5-yl)benzoate (Tz-Vis precursor)

Scheme S5. General reaction scheme of the synthesis of 11-hydroxyundecyl 4-(2-(pyren-1-yl)-2H-tetrazol-5-

yl)benzoate (Tz-Vis precursor).

0.258 g 1-aminopyrene (1.19 mmol, 1.0 equiv.) was dissolved in 30 mL THF and cooled to

-21°C under an argon atmosphere. In a second round bottom flask 1.07 g sodium

tetrafluoroborate (9.76 mmol, 8.1 eq.) was dissolved in 10.5 mL tetrafluoroboric acid (50 wt%)

and in 4.5 mL water under an argon atmosphere. This solution was slowly added to the

aminopyrene solution and stirred for 20 min at -21°C. Subsequently, 97.0 mg sodium nitrite

12
(1.41 mmol, 1.21 equiv.) was dissolved in a third round bottom flask in 2 mL water. The sodium

nitrite solution was slowly combined to form an orange precipitate. The reaction mixture was

stirred for another 20 minutes at -21°C. In parallel, 0.7 g compound (2) (1.43 mmol, 1.3 eq.)

was dissolved in 20 mL pyridine and cooled to 0 °C. The orange diazonium salt formed

previously was collected and added to the pyridine solution. The combined reaction mixture

was stirred for 1 h and then precipitated into 100 mL of a 1 M hydrochloric acid solution. The

raw product was recrystallized once from acetonitrile. After drying under high vacuum,

compound (5) was obtained as a brown solid (232 mg, yield 35%). 1H NMR (600 MHz , CDCl3)

δ [ppm] = 8.35 – 7.99 (m, 13 H), 4.32 – 4.28 (t, 2 H), 3.54 – 3.57 (t, 2 H), 1.75 – 1.70 (m, 2 H),

1.54 – 1.46 (m, 2 H), 1.40 -1.36 (m, 2 H), 1.32 – 1.17 (m, 13 H); 13C NMR (151 MHz , CDCl3)

δ [ppm] = 166.1, 165.6, 132.8, 132.3, 131.1, 131.0, 130.5, 130.3, 130.1, 130.1, 129.4, 129.0,

127.1, 127.0, 126.9, 126.7, 126.3, 125.1, 124.9, 124.8, 124.0, 122.7, 121.4, 65.5, 63.1, 32.8,

29.6, 29.5, 29.4, 29.3, 28.7, 26.1, 25.8 (Figure S7 and Figure S8).

u t
b d f h j l m v s
a
n w
c e g i k r
m
n q
o p

b
m-w
l
a, e - j

CDCl3

k c
d

9 8 7 6 5 4 3 2 1 0
/ ppm
Figure S7. 1H NMR spectrum (600 MHz, 256 scans, CDCl3) of 11-hydroxyundecyl 4-(2-(pyren-1-yl)-2H-tetrazol-
5-yl)benzoate (Tz-Vis precursor, 5): δ 8.37 – 8.31 (m, 2H), 8.28 (dd, J = 8.7, 5.1 Hz, 2H), 8.25 – 8.08 (m, 6H),
8.07 – 7.97 (m, 2H), 4.29 (t, J = 6.7 Hz, 2H), 3.55 (t, J = 6.6 Hz, 2H), 1.73 (p, J = 6.8 Hz, 2H), 1.48 (dt, J = 8.1,
6.5 Hz, 2H), 1.43 – 1.35 (m, 2H), 1.28 (s, 1H), 1.33 – 1.24 (m, 1H), 1.22 (s, 4H), 1.22 (s, 1H).

13
 ab z
ac y
a c e g i k m n ad
ah x
o ae
b j l ag w
d f h q af
n p
o r u v
s t

m - ah d-h

a b, j c, i

l q

200 180 160 140 120 100 80 60 40 20 0

/ ppm
Figure S8. 13C NMR spectrum (600 MHz, 1024 scans, CDCl3) of 11-hydroxyundecyl 4-(2-(pyren-1-yl)-2H-
tetrazol-5-yl)benzoate (Tz-Vis precursor, 5).

Synthesis of 11-(acryloyloxy)undecyl 4-(2-(pyren-1-yl)-2H-tetrazol-5-yl)benzoate (Tz-Vis

monomer)

Scheme S6. General reaction scheme of the synthesis of 11-(acryloyloxy)undecyl 4-(2-(pyren-1-yl)-2H-tetrazol-

5-yl)benzoate (Tz-Vis monomer).

In a flame dried schlenk flask, 1.38 g (2.47 mmol, 1.0 eq.) compound (5) and 5.3 mL (37.99

mmol, 15.4 eq.) triethylamine were dissolved in 150 mL of dry THF and subsequently cooled

to 0 °C. 3.4 mL (41.69 mmol, 16.8 eq.) acryloyl chloride was slowly added under an inert

atmosphere. The reaction was stirred for three hours at 0 °C and then over night at ambient

temperature. The salt was filtered out and the solvent was evaporated under reduced pressure.

The crude product was purified by flash chromatography (silica gel, cyclohexane/ethyl acetate,

14
70/30 v/v) to obtain 0.61 g of a pink powder (yield 40.2 %). 1H NMR (600 MHz , CDCl3) δ

[ppm] = 8.39- 8.05 (m, 13 H), 6.34 – 6.31 (d/d, 1 H), 6.07 – 6.02 (d/d, 1 H), 5.75 – 5.73 (d/d,

1 H), 4.32 – 4.28 (t, 2 H), 4.09 – 4.07 (t, 2 H), 1.77 – 1.72 (m, 2 H), 1.62 – 1.58 (m, 2 H), 1.43

-1.38 (m, 2 H), 1.32 – 1.19 (m, 12 H); 13C NMR (151 MHz , CDCl3) δ [ppm] = 166.32, 164.5,

131.2, 130.4, 130.3, 130.1, 129.4, 128.7, 127.1, 126.9, 126.8, 126.4, 125.2, 125.1, 124.8, 124.2,

122.8, 121.5, 65.5, 64.7, 29.5, 29.3, 28.7, 28.6, 26.1, 25.9 (Figure S9). HRMS [M+Na]+ m/z:

calcd for C38H38N4O4, Na+ 637.2792 found 637.2788.

15
 w v
CDCl3 a d f h j l n o x u
b p y
c e g i k m t
o
p s
q r

H2 O

g-l
o-y
d

b a f
c me

9 8 7 6 5 4 3 2 1 0

/ ppm

ae ad
a d f h j l n q ag af ak ac
p r ab
c o ah ai
b e g i k m s aj z
q u
r t x y
v w

CDCl3

e-m
a,b, q - ak

dn

c, o , t s
pu

200 180 160 140 120 100 80 60 40 20 0

/ ppm

Figure S9. 1H NMR (600 MHz, 256 scans, CDCl3) spectrum of 11-(acryloyloxy)undecyl 4-(2-(pyren-1-yl)-2H-
tetrazol-5-yl)benzoate (Tz-Vis monomer, 6): δ 8.50 – 8.12 (m, 11H), 6.35 (dd, J = 17.3, 1.6 Hz, 1H), 6.10 (dd, J =
17.3, 10.4 Hz, 1H), 5.79 (dd, J = 10.4, 1.6 Hz, 1H), 4.36 (t, J = 6.7 Hz, 2H), 4.12 (t, J = 6.7 Hz, 2H), 1.88 – 1.76
(m, 2H), 1.66 (p, J = 6.8 Hz, 2H), 1.53 (s, 10H), 1.29 (d, J = 23.4 Hz, 13H). 13C NMR (600 MHz, 1024 scans,
CDCl3) spectrum of 11-(acryloyloxy)undecyl 4-(2-(pyren-1-yl)-2H-tetrazol-5-yl)benzoate (Tz-Vis monomer, 6).

16
1.5. Miniemulsion

For a typical miniemulsion, the oil phase was prepared by adding MMA (0.9 g, 8.99 10-3 mole,

9 wt % rel. to water) , HD (0.072 g, 3.18 10-4 mole, 8 wt % rel. to monomer), 1,2-dichloroethane

(0.1 g, 1.01 10-3 mole, 1 wt% rel. to water), AIBN (1.8 mg, 1.07 10-5 mole, 0.01 M rel. to the

organic phase) and the tetrazole (Tz) monomer (variable weight, depending on recipe; 2.5 wt%

up to 10 wt % rel. to monomer) to a small glass vial with a stirring bar. The vial was completely

covered in aluminium foil and the Tz monomer was added as the last reagent. The solution was

stirred at 300 rpm for 30 min at room temperature. Next, the oil phase was added to the water

phase which was prepared in a vial (20 mL) covered with aluminium foil and consisted of Milli-

Q water (10 g, 5.55 10-1 mole) and SDS (0.08 g, 2.70 10-4 mole, 8 wt % rel. to the organic

phase) premixed at 300 rpm for 30 min. The mixture was homogenized by ultrasonication

(Branson Digital Sonifier) in an ice bath at 50% amplitude for 10 min. The miniemulsion was

kept in the vial, with a stirring bar and sealed with a rubber septum, parafilm and steel wire.

The vial was degassed for 30 min under nitrogen in an ice bath, and subsequently placed in a

preheated oil bath (70 °C). Polymerization was conducted for 24 h under nitrogen atmosphere,

completely shielded from light. After 24 h, the vial was taken out of the oil bath, opened to the

air and the polymerization was stopped by placing the vial in liquid nitrogen. Conversion

measurements were performed by taking a 2 mL aliquot from the vial immediately after

stopping the polymerization.

1.6. NITEC/NICAL reaction

The latexes were irradiated in a Luzchem LZC-4V photoreactor using 6 LZC-UVB lamps,

emitting at 300 nm (Figure S10) or 3 x 3W Blue LED emitting at 415 nm (Figure S11). The

17
internal chamber was ventilated to maintain ambient temperature during the entire experiment.

The samples were stirred employing the built-in LZC-D recessed magnetic stirrer.

1.2 1.2
1.0

Relative intensity
1.0 0.8

Relative intensity
0.6

0.8 0.4
0.2

0.6 0.0
250 300 350 400

Wavelength (nm)
0.4
0.2
0.0
200 300 400 500 600 700
Wavelength (nm)

Figure S10. Picture of the set-up for the UV-B reaction (left) and emission spectrum (right)

0.25 0.25

0.20
0.20
0.15
W m -2
W m-2 nm-2

0.15 0.10

0.05
0.10 0.00
380 390 400 410 420 430 440 450 460 470
0.05 Wavelength (nm)

0.00
400 450 500 550 600 650 700 750
Wavelength (nm)

Figure S11. Picture of the set-up for the visible reaction (left) and emission spectrum of the 3 x 3W Blue LED
(right)

UV-tetrazole

In a typical recipe, 0.0085 g N(-4-bromophenyl)-maleimide (0.0337 mmol, 1.0 eq.) was diluted

in 2.00 mL of water. 2.00 mL (2.18 g) latex containing 10 wt% Tz-UV (0.0335 mmol Tz-UV,

1.0 eq.) was added and the mixture was stirred for 10 minutes. The stock solution was divided

in 12 GPC vials (1.5 mL, 32 x 11.6 mm, clear glass, flat bottom, VWR) and exposed to UV-B

light (300 nm) for preset time intervals (1 to 120 minutes). Following irradiation, a 10 µL

aliquot of each sample was analyzed by UV and fluorescence spectroscopy after 250-fold

18
dilution. Half of the latex was centrifuged (14 500 rpm, 5 minutes) and the precipitate washed

with water twice. The precipitate was then dried under reduced pressure and pressed on Indium

foil for XPS analysis. The rest of the sample was evaporated under reduced pressure and the

dry latex was dissolved in CD2Cl2 for 1H NMR analysis.

Visible tetrazole

In a typical recipe, 0.0074 g N(-4-bromophenyl)-maleimide (0.029 mmol, 1.0 eq.) was diluted

in 2.00 mL of water. 2.00 mL (2.21 g) latex containing 10 wt% Tz-Vis (0.028 mmol Tz-Vis,

1.0 eq.) was added and the mixture was stirred for 10 minutes. The stock solution was divided

in 12 GPC vials (1.5 mL, 32 x 11.6 mm, clear glass, flat bottom, VWR) and exposed to 3 x 3W

Blue LED (415 nm) for preset time intervals (1 to 120 minutes). Following irradiation, a 10 µL

aliquot of each latex was analyzed by UV and fluorescence spectroscopy after 250-fold dilution.

Half of the latex was centrifuged (14 500 rpm, 5 minutes) and the precipitate washed with water

twice. The precipitate was then dried under reduced pressure and pressed on Indium foil for

XPS analysis. The rest of the sample was evaporated under reduced pressure and the dry latex

was dissolved in CD2Cl2 for 1H NMR analysis.

Small test reaction

0.00993 g 11-hydroxyundecyl 4-(2-(pyren-1-yl)-2H-tetrazol-5-yl)benzoate - Tz-Vis precursor,

5 – (0.017 mmol, 1.0 eq.) and 0.00449 g BVA (0.024 mmol, 1.4 eq.) were dissolved in 40 mL

of DCM. The tetrazole stock solution was degassed with argon for 10 minutes. 5 mL was

transferred into a vial and irradiated with 3 x 3W Blue LED (415 nm) for 60 minutes. Following

irradiation, a 50 µL aliquot was analyzed by fluorescence spectroscopy after 100-fold dilution.

The rest of the sample was evaporated under reduced pressure and the crude solid was dissolved

in CDCl3 for 1H NMR analysis.

19
0.00137 g 11-hydroxyundecyl 4-(2-(pyren-1-yl)-2H-tetrazol-5-yl)benzoate - Tz-Vis precursor,

5 – (0.002 mmol, 1.0 eq.) and 0.00135 g folic acid (0.003 mmol, 1.3 eq.) were dissolved in 1

mL of DMSO-d6. The sample was then irradiated with 3 x 3W Blue LED (415 nm) for 60

minutes. Following irradiation, a 10 µL aliquot was analyzed by fluorescence spectroscopy

after 300-fold dilution in DMSO. 1H NMR spectra were recorded on the crude sample.

2. Analysis results of the polymer latexes prepared using varying UV light Tz amounts.

Figure S12. ESI-MS of Tz-UV monomer in THF / MeOH (3/2 v/v%) after 10 min of ultra sonication at 50 %
intensity using a high shear probe.

Table S1. ESI-MS masses of Tz-UV monomer in THF / MeOH (3/2 v/v%) after 10 min of ultra sonication at 50
% intensity using a high shear probe.

Theoretical Experimental Δ m/z Peak

m/z m/z
521.2719 521.2750 0.0031 [M+H]+
543.2592 543.2579 0.0013 [M+Na]+
1063.5244 1063.5254 0.001 [2M+Na]+

20
 a d f h j l n o
b p q r
c e g i k m
o
p
q r s

H2O

CD2Cl2

n d f-l
opq r
b c a
m e

10 8 6 4 2 0

(ppm)

Figure S13. 1H NMR spectrum (400 MHz, CD2Cl2) of Tz-UV monomer. NMR was taken after treatment of the
monomer for 10 min of ultra-sonication at 50 % intensity using a high shear probe. δ 8.39 – 8.32 (m, 2H), 8.26 –
8.11 (m, 4H), 7.18 – 7.10 (m, 2H), 6.39 (dd, J = 17.3, 1.6 Hz, 1H), 5.83 (dd, J = 10.4, 1.6 Hz, 1H), 4.38 (t, J = 6.7
Hz, 2H), 4.15 (t, J = 6.7 Hz, 2H), 3.94 (s, 3H), 1.88 – 1.77 (m, 2H), 1.73 – 1.65 (m, 2H), 1.57 (s, 7H), 1.51 (p, J =
6.8 Hz, 2H), 1.35 (s, 7H), 1.32 (d, J = 18.1 Hz, 1H).

Table S2. Miniemulsion droplet diameter data (DLS; before polymerization) after 10 min ultra sonication at 50 %
intensity using a high shear probe. Each run consisted of 10 measurements with 5 runs in total of which the average
of each measurement is displayed below.

Zaverage Iaverage Vaverage Naverage PDI

nm nm Nm nm
PMMA 98 ± 3 105 ± 4 85 ± 3 67 ± 1 0.1 ± 0.01
2.5 wt% Tz-UV 48 ± 2 97 ± 37 39.5 ± 14 20 ± 7 0.257 ± 0.022
5 wt% Tz-UV 39 ± 1 93 ± 38 49 ± 7 21 ± 1 0.249 ± 0.038
7.5 wt% Tz-UV 71 ± 20 90 ± 40 36 ± 9 30 ± 3 0.340 ± 0.02
10 wt% Tz-UV 234 ± 40 191 ± 11 60 ± 30 30 ± 2 0.400 ± 0.028

Table S3. Polymer particle diameter data (DLS) after 24 h of polymerization at 70 °C. Each run consisted of 10
measurements with 5 runs in total of which the average of each measurement is displayed below.

Zaverage Iaverage Vaverage Naverage PDI

nm nm nm nm
PMMA 88 ± 3 184 ± 10 192 ± 12 55 ± 3 0.17 ± 0.01
2.5 wt% Tz-UV 115 ± 1 134 ± 2 108 ± 4 73 ± 3 0.125 ± 0.013
5 wt% Tz-UV 120 ± 3 155 ± 6 98 ± 10 47 ±11 0.208 ± 0.021
7.5 wt% Tz-UV 171 ± 15 232 ± 25 166 ± 45 60 ± 12 0.240 ± 0.024
10 wt% Tz-UV 167 ± 4 198 ± 21 174 ± 50 75 ± 10 0.22 ± 0.013

21
 Intensity
Number
Volume

1 10 100 1000 10000

Diameter (nm)
Figure S14. Particle size distributions based on intensity, number and volume for PMMA-Tz-UV (containing 2.5
wt % Tz) particles formed after 24 h of polymerization at 70 °C.
Molar Absorptivity (L·mol-1·cm-1)

10000
PMMA
2.5 wt% Tz
5.0 wt% Tz
7500 7.5 wt% Tz
10 wt% Tz

5000

2500

0
250 275 300 325 350
Wavelength (nm)

Figure S15. UV-Vis measurements of the PMMA latex (black lines) and PMMA Tz-UV latexes (colored lines)
of highly diluted translucent latex solutions with a maximum absorbance of 293 nm.

22
 1.2

1.0

Normalized (a.u.)
0.8

0.6

0.4

0.2
PMMA
PMMA-Tz-UV (10 wt%)
0.0
1800 1600 1400 1200 1000 800
Wavenumber (cm-1)

Figure S16. FT-ATR of dried PMMA latex (black line) and PMMA-Tz-UV (10 wt %) latex (dashed line). The
carbonyl peak (C=O at 1700 cm-1) is taken as a reference peak.

1.00
PMMA
2.5 wt% Tz
5.0 wt% Tz
0.75 7.5 wt% Tz
10 wt% Tz
w(logM)

0.50

0.25

0.00
10000 100000 1000000 1E7

M (g mol-1)

Figure S17. SEC distributions of dried PMMA latex (black line) and PMMA-Tz-UV latexes (colored lines)
measured in THF against PMMA calibration standards.

Table S4. SEC and conversion results of dried PMMA latex and PMMA-Tz-UV latexes. SEC traces are shown in
Figure S17.

Mn Mw Ð Conversion
-1 -1
g mol g mol %
PMMA 1 420 300 2 806 000 2.0 91
2.5 wt% Tz-UV 625 700 1 402 900 2.34 93
5 wt% Tz-UV 706 600 1 390 800 1.97 90
7.5 wt% Tz-UV 339 400 2 007 800 3.34 94
10 wt% Tz-UV 330 500 1 348 600 4.08 94

23
 t a
c b

d
u e
f b c t
g
h
i
j
k s u a f-m
m l

o n
p
o
p

q CD2Cl2
q
r
r

n d e
opq r

10 8 6 4 2 0

(ppm)
Figure S18. 1H NMR spectrum of dried PMMA-Tz-UV (containing 2.5 wt% Tz-UV) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

t a
c b

d
u e
f
g
h
i
j
k
m l s u
b c t
o n a f-m
p
o
p

q
q
r
r

s
CD2Cl2

n d e

opq r

10 8 6 4 2 0

(ppm)
Figure S19. 1H NMR spectrum of dried PMMA-Tz-UV (containing 5 wt% Tz-UV) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

24
 t a
c b

d a f-m
u e
f
b c t
g
h
i
j
k
m l

o n
s u
p
o
p

q
q
r
r

s
CD2Cl2

n d e

opq r

10 8 6 4 2 0

(ppm)
Figure S20. 1H NMR spectrum of dried PMMA-Tz-UV (containing 7.5 wt% Tz-UV) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

t a
c b

d
u e
f
g
h
i
k
j b c t
m l

o n
p s u
o
p
a f-m

q
q
r
r

CD2Cl2

n d e

opq r

10 8 6 4 2 0
(ppm)

Figure S21. 1H NMR spectrum of dried PMMA-Tz-UV (containing 10 wt% Tz-UV) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

25
 e-m
y z2

CD2Cl2

d n

a z
b z1

z3 c o t x ps u
qrv w

z3 c o t x

200 180 160 140 120 100 80 60 40 20 0

(ppm)

Figure S22. 13C NMR spectrum of dried PMMA-Tz-UV latex (containing 10 wt% Tz-UV) recorded in CD2Cl2 by
using 256 scans on a 400 MHz Bruker.

A B C

D E

Figure S23. TEM images of PMMA latex (A) and PMMA-Tz-UV latexes (2.5 wt% B; 5.0 wt% C; 7.5 wt% D;
10 wt% E) using 2 wt% osmium vapor (OsO4) staining.

26
 A
4400

4300

Counts (s)
4200

4100

4000

410 408 406 404 402 400 398 396 394 392

Binding Energy (eV)

B C

4500
4000

4400

Counts (s)
3900
Counts (s)

4300

3800 4200

4100
3700

410 408 406 404 402 400 398 396 394 392 410 408 406 404 402 400 398 396 394 392

Binding Energy (eV) Binding Energy (eV)

D E
4500
4600
4400
4500
4300
4400
Counts (s)
Counts (s)

4200
4300
4100
4200
4000
4100
3900
4000

3800
3900
410 408 406 404 402 400 398 396 394 392
410 408 406 404 402 400 398 396 394 392
Binding Energy (eV) Binding Energy (eV)

Figure S24. High resolution XPS scans of Nitrogen (N1s) of the dried PMMA reference samples (A) and PMMA-
Tz-UV latexes (2.5 wt% B; 5.0 wt% C; 7.5 wt% D; 10 wt% E). The atomic percentage of nitrogen at the surface
of each sample was calculated by integration of the raw peaks, without mathematical treatment. The reference
peak for charge compensation is the C-C peak at 284 eV.

27
3. Analysis results of the polymer latexes using 10 wt% UV light Tetrazole and varying

amounts of SDS.

Table S5. Miniemulsion droplet diameter data (DLS; before polymerization) after 10 min ultra sonication at 50 %
intensity using a high shear probe. Each run consisted of 10 measurements with 5 runs in total of which the average
of each measurement is displayed below.

Zaverage Iaverage Vaverage Naverage PDI

nm nm nm nm
PMMA 98 ± 3 105 ± 4 85 ± 3 67 ± 1 0.1 ± 0.01
6 wt % SDS 48 ± 2 136 ± 5 57 ± 2 27 ± 1 0.185 ± 0.01
8 wt% SDS 62 ± 3 128 ± 5 45 ± 2 20 ± 1 0.263 ± 0.02
10 wt% SDS 45 ± 2 142 ± 6 53 ± 3 26 ± 1 0.181 ± 0.02

Table S6. Polymer particle diameter data (DLS) after 24 h of polymerization at 70 °C. Each run consisted of 10
measurements with 5 runs in total of which the average of each measurement is displayed below.

Zaverage Iaverage Vaverage Naverage PDI

nm nm nm nm
PMMA 88 ± 3 184 ± 10 192 ± 12 55 ± 3 0.170 ± 0.01
6 wt % SDS 297 ± 8 815 ± 20 1355 ± 120 85 ± 2 0.564 ± 0.10
8 wt% SDS 167 ± 4 198 ± 21 174 ± 50 75 ± 8 0.220 ± 0.013
10 wt% SDS 524 ± 11 356 ± 25 189 ± 47 81 ± 7 0.321 ± 0.02

1.00
PMMA
6 wt% SDS
8 wt% SDS
0.75 10 wt% SDS
w(logM)

0.50

0.25

0.00
1000 10000 100000 1000000 1E7
-1
M (g·mol )
Figure S25. SEC of dried PMMA latex (black line) and PMMA-Tz-UV latexes (colored lines) measured in THF
against PMMA calibration standards.

28
Table S7. SEC and conversion results of dried PMMA latex and PMMA-Tz-UV latexes. SEC traces are shown in
Figure S25.

Mn Mw Ð Conversion
-1 -1
g mol g mol %
PMMA 1 420 300 2 806 000 2.0 91
6 wt % SDS 491 200 1 450 800 2.9 99
8 wt% SDS 281 600 2 358 000 5.1 98
10 wt% SDS 258 100 1 438 000 5.5 94

3800 4600

A 4500
B
3700

4400
3600
Counts (s)

Counts (s)
4300
3500
4200
3400
4100

3300
4000

3200 3900
410 408 406 404 402 400 398 396 394 392 410 408 406 404 402 400 398 396 394 392
Binding Energy (eV) Binding Energy (eV)

4800

4700
C
4600

4500
Counts (s)

4400

4300

4200

4100

4000

410 408 406 404 402 400 398 396 394 392

Binding Energy (eV)

Figure S26. High resolution XPS scans of nitrogen (N1s) of the PMMA-Tz-UV latexes (6 wt% SDS A; 8 wt%
SDS B; 10 wt% SDS C). The atomic percentage of nitrogen at the surface of each sample was calculated by
integration of the raw peaks, without mathematical treatment. The reference peak for charge compensation is the
C-C peak at 284 eV.

29
3. Analysis results of the polymer latexes prepared using varying Visible light Tz amounts.

500 1000 1500 2000

m / z (g·mol-1)

Figure S27. ESI-MS of Tz-Vis monomer in THF / MeOH (3/2 v/v%) after 10 min of ultra sonication at 50 %
intensity using a high shear probe.

Table S8. ESI-MS masses of Tz-Vis monomer in THF / MeOH (3/2 v/v%) after 10 min of ultra sonication at 50
% intensity using a high shear probe.

Theoretical Experimental Δ m/z Peak

m/z m/z
637.2750 637.2763 0.0013 [M+Na]+
1251.5621 1251.5636 0.0015 [2M+Na]+

n r
d f h j l o p q
c
e g i k m o
b s
a p q r

H2O

CD2Cl2

o -s n d f-l

b c a m e

10 8 6 4 2 0

(ppm)
Figure S28. 1H NMR spectrum (400 MHz, CD2Cl2) of Tz-Vis monomer. NMR was taken after treatment of the
monomer for 10 min of ultra-sonication at 50 % intensity using a high shear probe. δ 8.50 – 8.12 (m, 11H), 6.35
(dd, J = 17.3, 1.6 Hz, 1H), 6.10 (dd, J = 17.3, 10.4 Hz, 1H), 5.79 (dd, J = 10.4, 1.6 Hz, 1H), 4.36 (t, J = 6.7 Hz,
2H), 4.12 (t, J = 6.7 Hz, 2H), 1.88 – 1.76 (m, 2H), 1.66 (p, J = 6.8 Hz, 2H), 1.53 (s, 10H), 1.29 (d, J = 23.4 Hz,
13H).

30
Table S9. Miniemulsion droplet diameter data (DLS; before polymerization) after 10 min ultra sonication at 50
% intensity using a high shear probe. Each run consisted of 10 measurements with 5 runs in total of which the
average of each measurement is displayed below.

Zaverage Iaverage Vaverage Naverage PDI

nm nm nm nm
PMMA 98 ± 3 105 ± 4 85 ± 3 67 ± 1 0.1 ± 0.01
2.5 wt% Tz-Vis 43 ± 2 193 ± 5 54 ± 2 20 ± 1 0.228 ± 0.02
5 wt% Tz-Vis 56 ± 2 206 ± 4 45 ± 2 22 ± 1 0.355 ± 0.1
7.5 wt% Tz-Vis 58 ± 1 316 ± 7 127 ± 5 32 ± 2 0.322 ± 0.08
10 wt% Tz-Vis 89 ± 2 104 ± 2 46 ± 3 27 ± 2 0.249 ± 0.04

Table S10. Polymer particle diameter data (DLS) after 24 h of polymerization at 70 °C. Each run consisted of 10
measurements with 5 runs in total of which the average of each measurement is displayed below.

Zaverage Iaverage Vaverage Naverage PDI

nm nm nm nm
PMMA 88 ± 3 184 ± 10 192 ± 12 55 ± 3 0.17 ± 0.01
2.5 wt% Tz-Vis 149 ± 8 187 ± 11 209 ± 15 74 ± 4 0.204 ± 0.02
5 wt% Tz-Vis 106 ± 7 159 ± 11 135 ± 8 37 ± 2 0.215 ± 0.01
7.5 wt% Tz-Vis 164 ± 9 251 ± 14 320 ± 21 74 ± 3 0.228 ± 0.03
10 wt% Tz-Vis 111 ± 6 200 ± 10 130 ± 7 31 ± 2 0.289 ± 0.03

Intensity
Number
Volume

1 10 100 1000 10000

Diameter (nm)
Figure S29. Particle size distributions based on intensity, number and volume for PMMA-Tz-Vis (containing 2.5
wt % Tz) particles formed after 24 h of polymerization at 70 °C.

31
 Molar Absorptivity (L·mol-1·cm-1) 1000
PMMA 1.00 PMMA
2.5 wt% Tz Tz-Vis monomer
5.0 wt% Tz PMMA Tz-Vis
750 7.5 wt% Tz

Fluorescence (a.u.)
0.75
10 wt% Tz

500
0.50

250
0.25

0
0.00
260 280 300 320 340 360 380 400 400 450 500 550 600 650
Wavelength (nm) Wavelength (nm)
Figure S30. UV-Vis (left) and Fluorescence (right) measurements of the PMMA latex (black line) and PMMA-
Tz-Vis latexes (colored lines) of highly diluted translucent latex solutions with a maximum absorbance and
emission of 348 nm and 432 nm respectively.

1.50

1.25
Intensity (a.u.)

1.00

0.75

0.50

0.25
PMMA
Tz-Vis monomer
0.00
PMMA Tz-Vis

1800 1600 1400 1200 1000 800

-1
Wavenumber (cm )
Figure S31. FT-ATR of dried PMMA latex (solid line), Tz-Vis monomer (dashed line) PMMA-Tz-Vis (10 wt %)
latex (dotted line). De carbonyl peak (C=O at 1700 cm-1) is taken as a reference peak.

1.00
PMMA
2.5 wt% Tz
5.0 wt% Tz
0.75 7.5 wt% Tz
10 wt% Tz
w(logM)

0.50

0.25

0.00
10000 100000 1000000 1E7
-1
M (g mol )

Figure S32. SEC of dried PMMA latex (black line) and PMMA-Tz-Vis latexes (colored lines) measured in THF
against PMMA calibration standards.

32
Table S11. SEC and conversion results of dried PMMA latex and PMMA-Tz-Vis latexes. SEC traces are shown
in Figure S32.

Mn Mw Ð Conversion
-1 -1
g mol g mol %
PMMA 1 420 300 2 806 000 2.0 91
2.5 wt% Tz-Vis 1 126 000 1 694 000 1.6 95
5.0 wt% Tz-Vis 345 600 1 618 000 4.7 98
7.5 wt% Tz-Vis 258 800 1 090 000 4.2 99
10 wt% Tz-Vis 420 400 1 280 000 3.0 92

t a
c b

d
u e
f
g
h
i
j
k
m l
u b c t
o n
p a f-m

q
r CD2Cl2
s

o -s d e

10 8 6 4 2 0
(ppm)
Figure S33. 1H NMR spectrum of dried PMMA-Tz-Vis (containing 2.5 wt% Tz-Vis) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

33
 t a
c b

d
u e
f
g
h
i
j
k
m l
u b c t
o n
p a f-m

q
r CD2Cl2
s

o -s d e

10 8 6 4 2 0

(ppm)
Figure S34. 1H NMR spectrum of dried PMMA-Tz-Vis (containing 5 wt% Tz-Vis) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

t a
c b

d
u e
f
g
h
i
j
k
m l
u b c t
o n
p a f-m

q
r CD2Cl2
s

o -s d e

10 8 6 4 2 0
(ppm)
Figure S35.1H NMR spectrum of dried PMMA-Tz-Vis (containing 7.5 wt% Tz-Vis) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

34
 t a
c b

d
u e
f
g
h
i
j
k
l
m
u b c t
o n
p a f-m

q
r CD2Cl2
s

o -s d e

10 8 6 4 2 0
(ppm)
Figure S36. 1H NMR spectrum of dried PMMA-Tz-Vis (containing 10 wt% Tz-Vis) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

z a
z1 b

z3 c

d
z2 e
f
g
h
i
j
k
m l

q n CD2Cl2
r o
p
t s
z2
u
v
e-m
x
y

d n

a z
b z3

z3 t - y
o c p-s

220 200 180 160 140 120 100 80 60 40 20 0

(ppm)
Figure S37. 13C NMR spectrum of dried PMMA-Tz-Vis (containing 10 wt% Tz-Vis) latex recorded in CD2Cl2 by
using 64 scans and 12 s delay on a 400 MHz Bruker.

35
 A B C

D E

Figure S38. TEM images of PMMA latex (A) and PMMA-Tz-Vis latexes (2.5 wt% B; 5.0 wt% C; 7.5 wt% D;
10 wt% E) using a 2 wt% osmium vapor (OsO4) staining for each sample.

A B

C D

Figure S39. SEM images of dried PMMA-Tz-Vis latexes (2.5 wt% B; 5.0 wt% C; 7.5 wt% D; 10 wt% E) using
double sided carbon tape and a 5 nm platinum coating for each sample.

36
 A B
4400
4300

4300
4200
Counts (s)

Counts (s)
4200
4100

4100
4000

4000
3900
410 408 406 404 402 400 398 396 394 392 410 408 406 404 402 400 398 396 394 392
Binding Energy (eV) Binding Energy (eV)

C D
4500 4600

4500
4400
4400
Counts (s)
Counts (s)

4300
4300

4200 4200

4100 4100

4000
4000
3900
410 408 406 404 402 400 398 396 394 392 410 408 406 404 402 400 398 396 394 392

Binding Energy (eV) Binding Energy (eV)

E
4000

3900

3800
Counts (s)

3700

3600

3500

3400

410 408 406 404 402 400 398 396 394 392

Binding Energy (eV)

Figure S40. High resolution XPS scans of Nitrogen (N1s) of the dried PMMA reference samples (A) and PMMA-
Tz-Vis latexes (2.5 wt% B; 5.0 wt% C; 7.5 wt% D; 10 wt% E) are presented. The atomic percentage of nitrogen
at the surface of each sample was calculated by integration of the raw peaks, without mathematical treatment. The
reference peak for charge compensation is the C-C peak at 284 eV.

37
4. Analysis results of the PMMA-Tz-UV after irradiation under UV-B light

s, u b, c, t
CD2Cl2 a, f-
d, m

t n e
c ba

u s, u
e d n
g f
h
i
k j s, u
m l 2 3
1
b, c, t
o n a, f-
p d, m
o op
p r e
q n
q 1
q
r 1 2
r 3
s 2 3

13 12 11 10 9 8 7 6 5 4 3 2 1 0
(ppm)

4 f
5
g
4 5 6 f f
g g 4 3
6 h 25 1 i j
h h 6
i i cf
j a b g 2 4 3
h 5 1 di

1 2
2 1 3
a
1 b a
2 3 a
b bc d
3
c c
d d

e e

10 9 8 7 6
(ppm)

Figure S41. 1H NMR of the PMMA-Tz-UV (10 wt%, UV4) copolymer after the NITEC reaction with N-BPM at
0 (bottom), 10 (middle) and 120 minutes (top) with the corresponding labels. Zoom in the aromatics region (6 to
10 ppm) below (600 MHz, 128 scans, 12 s delay, CD2Cl2)

38
 A B
550
1600
1550 500

Counts (s)
1500 450
Counts (s)

1450
400
1400
350
1350
1300 300
410 405 400 395 390 74 72 70 68 66 64 62 60
Binding Energy (eV) Binding Energy (eV)
C D
220

1400 200
180
Counts (s)
Counts (s)

1300
160
1200 140
120
1100
100
410 405 400 395 390 74 72 70 68 66 64 62 60
Binding Energy (eV) Binding Energy (eV)

Figure S42. High resolution XPS scans of Nitrogen (N1s) and Bromine (Br3d) of the dried and washed PMMA-
Tz-UV latexes (10 wt%, UV4) before (A – B) and after NITEC reaction with N-BPM (C – D) (120 minutes of
irradiation) are presented.

Table S12. Atomic percentage measured by XPS of the washed and dried PMMA-Tz-UV latexes (10 wt%, UV4)
after NITEC reaction with N-BPM at different time reaction. The atomic percentage at the surface of each sample
was calculated by integration of the raw peaks, without mathematical treatment. The average of two measurements
on different location of the same sample and standard deviation are presented.

Time (min) 0 10 60 120

atom%
0.00 ± 0.00 0.16 ± 0.06 0.27 ± 0.01 0.22 ± 0.01
Br3d
73.68 ± 0.22 74.75 ± 0.16 74.05 ± 0.07 76.05 ± 0.39
C1s
1.04 ± 0.05 0.90 ± 0.04 0.86 ± 0.06 0.74 ± 0.00
N1s
25.26 ± 0.20 23.72 ± 0.58 23.62 ± 0.60 22.99 ± 0.38
O1s
S1s 0.00 ± 0.00 0.36 ± 0.36 0.05 ± 0.05 0.00 ± 0.00

39
 (A) (B)
300
Fluorescence Intensity (a.u.)

Fluorescence Intensity (a.u.)

10 wt% 5 wt%
NITEC - N-BPM NITEC - HEA
250
7.5 wt% 2.5 wt% 1000 NITEC - NEM NICAL - BVA

200 800

150 600

100 400

50 200
0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)

Figure S43. (A) Kinetic plots displaying the fluorescence emission vs. reaction time for the NITEC reaction of N-
BPM and latexes containing 2.5 wt% (triangle up, UV1), 5 wt% (square, UV2), 7.5 wt% (triangle down, UV3)
and 10 wt% (circle, UV4) of Tz-UV (λex = 390 nm). (B) Fluorescence emission spectra of highly diluted PMMA-
Tz-UV (10 wt%) latex after the NITEC reaction with N-BPM, HEA and NEM at different reaction times (λex =
390 nm).

(A) 250 (B)

Fluorescence Intensity (a.u.)

400
Fluorescence Intensity (a.u.)

10 wt% 5 wt% 10 wt% 5 wt%

7.5 wt% 2.5 wt% 7.5 wt% 2.5 wt%
200
300
150
200
100

50 100

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)

Figure S44. Kinetic plots displaying the fluorescence emission vs reaction time for the NICAL reaction with BVA
(A) or the NITEC of HEA (B) and latexes containing 2.5 wt% (triangle up, UV1), 5 wt% (square, UV2), 7.5 wt%
(triangle down, UV3) and 10 wt% (circle, UV4) of Tz-UV (λex = 390 nm).

40
 (A1) (B)
0.5

Absorbance Intensity (a. u.)

t=0 t = 5 min
t = 1 min t = 10 min
0.4 t = 2 min t = 30 min
t = 3 min t = 60 min
t = 4 min t = 120 min
0.3

(A2) 0.2

0.1

0.0
300 400 500 600 700 800
Wavelength (nm)

(C) (D)
300
Fluorescence Intensity (a.u.)

t=0 t = 4 min t = 60 min

t = 1 min t = 5 min t = 120 min 1.2
250 N exp Br theo

Atomic percentage (%)

t = 2 min t = 10 min Atomic percentage (%) N theo Br exp 0.3
t = 3 min t = 30 min
200 1.0

150 0.2
0.8
100
0.6 0.1
50
0 0.4 0.0
450 500 550 600 650 0 20 40 60 80 100 120
Wavelength (nm) Time (min)

Figure S45. (A) Photographs of the PMMA-Tz-UV (10 wt%, UV4) latex after the NICAL reaction with BVA at
different reaction times (from left to right: 0, 1, 2, 3, 4, 5, 10, 30, 60 and 120 min) under white light (A1) and under
a hand-held UV lamp (λex = 365 nm) (A2). (B) UV-vis absorbance spectra of highly diluted PMMA-Tz-UV (10
wt%, UV4) latex after the NICAL reaction with BVA at different reaction times. (C) Fluorescence emission spectra
of highly diluted PMMA-Tz-UV (10 wt%, UV4) latex after the NICAL reaction with BVA at different reaction
times (λex = 390 nm). (D) Atomic percentage of Nitrogen (left y-axis) and Bromine (right y-axis) measured by
XPS on the surface of the dried copolymer after purification and theoretical content (Equation S1 and S2).

41
 CD2Cl2
t c a
b

u d b, c, t
e
g f
i h a, f-
k j m,
m l w-z
o n
p s, u
o
z x p
y w v
q
q
r r

s n d,
e
o pq r

12 11 10 9 8 7 6 5 4 3 2 1 0
/ ppm
Figure S46. 1H NMR of the PMMA-Tz-UV (10 wt%, UV4) copolymer after the NICAL reaction with BVA at
60 minutes with the corresponding labels (600 MHz, 128 scans, 12 s delay, CD2Cl2)

(A)

t = 60 min

t = 0 min

10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100-110
(B) / ppm
CD 2Cl2
t c a
t CD2Cl2 b
c ba

u d
u e
e d b, c, t g f
g f b, c, t
h i h
i k j
a, f-
k j m l
m
m l n
a, f-
o m
o n p
p o
o p
p
s, u v
q s, u
q q
q r
r r r d,
d,
s e s e

o pq r n n
o pq r

12 11 10 9 8 7 6 5 4 3 2 1 0 12 11 10 9 8 7 6 5 4 3 2 1 0
/ ppm / ppm

Figure S47. (A) 19F NMR of the PMMA-Tz-UV (10 wt%, UV4) copolymer after the NICAL reaction with TFA
at 0 (bottom), and 60 minutes (top) after purification of the copolymer (600 MHz, 12 s delay, 128 scans, CD2Cl2).
(B) 1H NMR of the PMMA-Tz-UV (10 wt%, UV4) copolymer after the NICAL reaction with TFA at 0 (left) and

42
60 minutes (right) after purification of the copolymer with the corresponding labels (600 MHz, 12s delay, 128
scans CD2Cl2).

Table S13. Atomic percentage measured by XPS of the washed and dried PMMA-Tz-UV latexes (10 wt%, UV4)
after NICAL reaction with BVA at different time reaction. The atomic percentage at the surface of each sample
was calculated by integration of the raw peaks, without mathematical treatment. The average of two measurements
on different location of the same sample and standard deviation are presented.

Time (min) 0 10 30 60 120

atom%
Br3d 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00
C1s 64.24 ± 0.65 73.55 ± 2.1 74.77 ± 0.08 76.26 ± 0.24 74.19 ± 0.12
N1s 1.09 ± 0.02 0.77 ± 0.10 0.61 ± 0.00 0.65 ± 0.04 0.70 ± 0.10
O1s 34.66 ± 0.62 25.68 ± 1.98 24.61 ± 0.09 23.08 ± 0.29 25.10 ± 0.02
S1s 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00

Table S14. Atomic percentage measured by XPS of the washed and dried PMMA-Tz-UV latexes (10 wt%, UV4)
after NICAL reaction with TFA at different time reaction. The atomic percentage at the surface of each sample
was calculated by integration of the raw peaks, without mathematical treatment. The average of two measurements
on different location of the same sample and standard deviation are presented.

Time (min) 0 60
atom%
F1s 0.00 ± 0.00 0.18 ± 0.01
C1s 73.66 ± 0.00 74.11 ± 0.34
N1s 1.00 ± 0.00 0.48 ± 0.01
O1s 25.34 ± 0.00 25.23 ± 0.34
S1s 0.00 ± 0.00 0.00 ± 0.00

Table S15. Atomic percentage measured by XPS of the dried PMMA-Tz-UV latexes (10 wt%, UV4) after NICAL
reaction with BVA at different time reaction (no purification). The atomic percentage at the surface of each sample
was calculated by integration of the raw peaks, without mathematical treatment.

Time (min) 0 10 30 60 120

atom(%)
Br3d 0.26 0.09 0.14 0.09 0.28
C1s 75.59 76.18 75.80 75.80 72.60
N1s 0.89 0.53 0.37 0.30 0.32
O1s 22.49 22.53 23.39 23.11 26.08
S1s 0.78 0.67 0.66 0.697 0.721

43
5. Analysis results of the PMMA-Tz-Vis after irradiation under visible light

t c a
b

u d
e
g f CD2Cl2

i h
k j
m l
o n 3
3
p a, f-
2 1 o m
p
1 b, c, t
y
q x
u
w
r
s v
t u d,
e
o-y 2
n

10 9 8 7 6 5 4 3 2 1 0
(ppm)

Figure S48. 1H NMR spectrum of dried PMMA-Tz-Vis (10 wt%, Vis4) copolymer after the NITEC reaction with NEM
at 120 minutes with the corresponding labels (600 MHz, 128 scans, 12 s delay, CD2Cl2)

44
A B
320

1600 300
280

Counts (s)
Counts (s)

1500
260
1400 240
220
1300
200
410 405 400 395 390 74 72 70 68 66 64 62 60
Binding Energy (eV) Binding Energy (eV)
C D
200
1600
180
1500 160
Counts (s)
Counts (s)

140
1400
120
1300
100

1200 80
410 405 400 395 390 74 72 70 68 66 64 62 60
Binding Energy (eV) Binding Energy (eV)
Figure S49. High resolution XPS scans of Nitrogen (N1s) and Bromine (Br3d) of the dried and washed PMMA-
Tz-Vis latexes (10 wt%, Vis4) before (A - B) and after NITEC reaction with N-BPM (C - D) (120 minutes of
irradiation) are presented.

Table S16. Atomic percentage measured by XPS of the washed and dried PMMA-Tz-Vis latexes (10 wt%, Vis4)
after NITEC reaction with N-BPM at different time reaction. The atomic percentage at the surface of each sample
was calculated by integration of the raw peaks, without mathematical treatment. The average of two measurements
on different location of the same sample and standard deviation are presented.

Time (min) 0 30 60 120

atom%
Br3d 0.00 ± 0.00 0.13 ± 0.01 0.14 ± 0.1 0.16 ± 0.01
C1s 75.69 ± 0.40 75.72 ± 0.14 75.72 ± 0.14 75.59 ± 0.46
N1s 1.07 ± 0.01 1.14 ± 0 0.97 ± 0.04 0.80 ± 0.05
O1s 23.24 ± 0.42 22.71 ± 0.98 23.12 ± 0.22 23.24 ± 0.38
S1s 0.00 ± 0.00 0.00 ± 0.00 0.04 ± 0.04 0.21 ± 0.03

45
 A B
1000

Fluorescence Intensity (a.u.)

1000
Fluorescence Intensity (a.u.)
t = 0 min t = 0 min
t = 1 min t = 5 min
800 t = 2 min 800 t = 10 min
t = 3 min t = 30 min
t = 5 min t = 60 min
600 t = 10 min 600 t = 120 min
t = 30 min
t = 60 min
400 t = 120 min 400

200 200

0 0
400 500 600 400 500 600
Wavelength (nm) Wavelength (nm)
C D
1000

Fluorescence Intensity (a.u.)

1000
Fluorescence Intensity (a.u.)

t = 0 min
t = 0 min
t = 5 min
t = 5 min
800 t = 10 min 800 t = 10 min
t = 30 min
t = 30 min
t = 60 min t = 60 min
600 t = 120 min
600 t = 120 min

400 400

200 200

0 0
400 500 600 400 500 600
Wavelength (nm) Wavelength (nm)

Figure S50. Fluorescence intensity of PMMA-Tz-Vis latexes (A - 10 wt%, B - 7.5 wt%, C - 5.0 wt% and D - 2.5
wt%) after NITEC reaction with NEM at different times reactions are presented (λex = 350 nm).

Table S17. Atomic percentage measured by XPS of the washed and dried PMMA-Tz-Vis latexes (10 wt%, Vis4)
after NICAL reaction with BVA after 120 minutes of irradiation. The atomic percentage at the surface of each
sample was calculated by integration of the raw peaks, without mathematical treatment. The average of two
measurements on different location of the same sample and standard deviation are presented.

Time (min) 0 120

Atom%
Br3d 0.00 ± 0.00 0.00 ± 0.00
C1s 74.04 ± 2.05 74.03 ± 2.05
N1s 0.94 ± 0.07 0.73 ± 0.07
O1s 31.11 ± 4.89 25.12 ± 1.99
S1s 0.00 ± 0.00 0.06 ± 0.06

46
Table S18. Atomic percentage measured by XPS of the dried PMMA-Tz-Vis latexes (10 wt%, Vis4) after NICAL
reaction with BVA after 120 minutes of irradiation (no purification). The atomic percentage at the surface of each
sample was calculated by integration of the raw peaks, without mathematical treatment. The average of two
measurements on different location of the same sample and standard deviation are presented.

Time (min) 0 10 60 120

atom%
Br3d 0.11 ± 0.02 0.12 ± 0.00 0.11 ± 0.0 0.12 ± 0.01
C1s 75.97 ± 0.18 75.83 ± 0.42 75.83 ± 0.45 75.72 ± 0.11
N1s 0.80 ± 0.03 0.78 ± 0.06 0.68 ± 0.07 0.64 ± 0.07
O1s 22.25 ± 0.16 22.38 ± 0.30 22.43 ± 0.52 22.59 ± 0.06
S1s 0.86 ± 0.03 0.89 ± 0.06 0.95 ± 0.00 0.92 ± 0.09

0.8
t = 0 min t = 0 min
1.2 t = 30 min
t = 30 min
Absorbance (a.u.) t = 60 min
Absorbance (a.u.)

1.0 t = 60 min 0.6

t = 120 min t = 120 min
0.8
0.4
0.6
0.4 0.2
0.2
0.0
0.0
300 400 500 600 300 400 500 600
Wavelength (nm) Wavelength (nm)

Figure S51. UV-vis absorbance of a folic acid solution (7.2 g L-1) after 2 h irradiation under UV-B light (300 nm)
(left) and under visible light (415 nm) (right).

47
 u H2O DMSO
b d f h j l m v s
m w
c e g i k n r
a q b
n a, e - j
2 3 o p
1
4 5 l
m-w 7 8
6 2
12 7 7
11 10
13 8 8 6
4 k cd
13
10 9 11
3
1
5 9 12
u s
b d f h j l m v r H2O DMSO
m14
c e g i k n w q
a p
n b
34 o
12 2 5
13 6 a, e - j
11 7
8 8
7 l
10 9 m-w 6
10 2
14 11 4
13 3 k cd
1 9 12
5

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
/ ppm

Figure S52. 1H NMR spectrum of the Visible-Tet precursor with folic acid before and after 1 h irradiation under
visible light with the corresponding labels (600 MHz, 12 s delay, 128 scans, DMSO-d6)

48