This README file was generated on 2023-09-12 by Julius Gemen.

GENERAL INFORMATION

1. Title of Dataset: Disequilibrating azobenzenes by visible-light sensitization under confinement
2. Author Information A. Principal Investigator Contact Information Name: Rafal Klajn
   Institution: Weizmann Institute of Science Address: Rehovot, Israel Email: rafal.klajn@weizmann.ac.il <br> B. Associate or Co-investigator Contact Information Name: Julius Gemen Institution: Weizmann Institute of Science Address: Rehovot, Israel Email: julius.gemen@weizmann.ac.il
3. Date of data collection (single date, range, approximate date): 2020-2023
4. Geographic location of data collection: Rehovot, Israel
5. Information about funding sources that supported the collection of the data: We acknowledge funding from the European Union’s Horizon 2020 Research and Innovation Program [European Research Council grants 820008 (R.K.) and 101045223 (A.P.) and Marie Skłodowska-Curie grants 812868 (J.G.) and 101022777 (T.P.R.)], the Academy of Finland [Center of Excellence Programme LIBER grant 346107 (A.P.), Flagship Programme PREIN grant 32016 (A.P.), and Postdoctoral Researcher grant 340103 (T.P.R.)], Zuckerman STEM Leadership Program Fellowship (J.R.C.), President’s PhD Scholarship (M.O.), and the EPSRC [Established Career Fellowship grant EP/R00188X/1 (M.J.F.)].

SHARING/ACCESS INFORMATION

1. Licenses/restrictions placed on the data: CC0 1.0 Universal (CC0 1.0) Public Domain
2. Links to publications that cite or use the data:

Preprint: https://doi.org/10.26.../chemrxiv-2023-gq2h0

1. Links to other publicly accessible locations of the data: None
2. Links/relationships to ancillary data sets: None
3. Was data derived from another source? No A. If yes, list source(s): NA
4. Recommended citation for this dataset:

Gemen, Julius et al. (2023). Disequilibrating azobenzenes by visible-light sensitization under confinement [Dataset]. Dryad. https://doi.org/10.5061/dryad.4qrfj6qg1

DATA & FILE OVERVIEW

1. File List:

A) Data_Summary_MS.xlsx
B) Data_Summary_SI.xlsx

1. Relationship between files, if important: None
2. Additional related data collected that was not included in the current data package: None
3. Are there multiple versions of the dataset? No A. If yes, name of file(s) that was updated: NA i. Why was the file updated? NA ii. When was the file updated? NA

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DATA-SPECIFIC INFORMATION FOR: Data_Summary_MS.xlsx

This file summarizes the data shown in figures 2-5 of the manuscript. A seperate sheet was set up for every relevant figure and labeled accordingly. Subfigures are seperated within a data sheet by a black bar.
The file contains obtained steady-state and transient UV-Vis and fluorescence spectrocopy data, computationally determined values, and other important data.
All data were collected in the laboratories of the authors. Please contact the corresponding authors directly if questions remain.

Sheet 1 (Fig. 2):
b - Absorption spectrum of a 1:1 mixture of (ps1)2⊂H and (E-1)2⊂H and changes in the spectra accompanying irradiation with green light (525 nm).
c - Absorption spectrum of a 1:1 mixture of (ps1)2⊂H and (E-9)2⊂H and changes in the spectra accompanying irradiation with green light (525 nm).
e - Graph following DESC of 9 in the presence of different equiv. of ps1 (the data were normalized to the 0 to 1 range, except the experiment with no PS)
f - Evolution of the emission intensity of ps1 under 515-nm light (used both to induce DESC and excite fluorescence) as a function of the amount of 9.
g - More than 100 cycles of reversible photoisomerization of 9 induced solely by visible light (E→Z, DESC with 525-nm light for 2 min; Z→E, direct photoexcitation using 435-nm light for 30 s). The amount of the E isomer is proportional to absorbance at 353 nm; the absorption at 480 nm originates from the (ps1)2⊂H homodimer.
Abbreviations:
b - wl = wavelength; t = time; s = second
c - wl = wavelength; t = time; s = second; w/o = without
e - min = minute; t = time
f - t = time; s = second
g - nm = nanometer

Sheet 2 (Fig. 3):
a - Normalized decays of fs transient absorption of ps1 at 412 nm and 483 nm within the (ps1)2⊂H homodimer (l_exc = 500 nm).
b - Normalized transient-absorption decays of ps1 at 483 nm (l_exc = 500 nm) in (ps1)2⊂H versus the (E-9·ps1)⊂H heterodimer.
c - Decays of us transient absorption at 430 nm (l_exc = 510 nm) in (ps1)2⊂H in the presence of increasing amounts of (E-9)2⊂H.
e - Ground-state relaxed scan along the C–N=N–C dihedral angle F in 1 within the 1·ps1 heterodimer.
f - Ground-state relaxed scan of F in 1 within the (1·ps1)⊂H heterodimer
Abbreviations:
a - time_r0-norm-bleach-483nm = time in nanoseconds; data_r0-norm-bleach-483nm = absorption difference at 483 nanometer (data); fit_r0-norm-bleach-483nm = absorption difference at 483 nanometer (fit); data_r0-norm-bleach-412nm = absorption difference at 412 nanometer (data); fit_r0-norm-bleach-412nm = absorption difference at 412 nanometer (fit)
b - time_r0-norm-bleach-483nm = time in nanoseconds; data_r0-norm-bleach-483nm = absorption difference at 483 nanometer (data); fit_r0-norm-bleach-483nm = absorption difference at 483 nanometer (fit); time_r2-norm-bleach-483nm = r2 time in nanoseconds; data_r2-norm-bleach-483nm = r2 absorption difference at 483 nanometer (data); fit_r2-norm-bleach-483nm = r2 absorption difference at 483 nanometer (fit)
c - ratio-time = time in milliseconds; r0-data = absorption difference at 430 nm for 0 eq (data); r0-fit = absorption difference at 430 nm for 0 eq (fit); r0.5-data = absorption difference at 430 nm for 0.5 eq (data); r0.5-fit = absorption difference at 430 nm for 0.5 eq (fit); r1-data = absorption difference at 430 nm for 1 eq (data); r1-fit = absorption difference at 430 nm for 1 eq (fit); r3-data = absorption difference at 430 nm for 3 eq (data); r3-fit = absorption difference at 430 nm for 3 eq (fit)e - no abbreviations
f - eV = electron volt

Sheet 3 (Fig. 4):
b - Changes in the absorption spectra of encapsulated E-4 in the presence of an equimolar amount of encapsulated sensitizer ps2 under yellow light (l ≈ 561 nm; 2.5 mW·cm–2).
c - DESC (here, for E-4) in the presence of substoichiometric amounts of ps2.
d - Changes in the absorption spectra of encapsulated E-1 in the presence of an equimolar quantity of encapsulated sensitizer ps3 under orange light (l ≈ 599 nm; 0.8 mW·cm–2).
e - DESC (here, for E-1) in the presence of substoichiometric amounts of ps3.
f - Changes in the absorption spectra of encapsulated E-2 in the presence of an equimolar quantity of encapsulated sensitizer ps4 under red light (l ≈ 635 nm; 3.4 mW·cm–2).
g - DESC (here, for E-2) in the presence of substoichiometric amounts of ps4.
Abbreviations:
b - wl = wavelength; t = time; s = second
c - t = time; min = minute
d - wl = wavelength; t = time; s = second
e - t = time; min = minute
f - wl = wavelength; t = time; s = second
g - t = time; min = minute

Sheet 4 (Fig. 5):
b - Red-light switching of E-3 dissolved in water in the presence of 0.005 equiv. of (ps4)2⊂H affords a PSS featuring 88% Z-3.
d - Absorption spectra: Selective switching of the negatively charged E-3 with 561-nm light in the presence of the positively charged E-5 on the micromolar scale.
f - Absorption spectra: Selective switching of E-4 with 561-nm light and (ps2)2⊂H in the presence of a UV-dimerizable anthracene.
Abbreviations:
b - wl = wavelength; t = time; min = minute
d - wl = wavelength; t = time; min = minute
f - wl = wavelength; t = time; min = minute

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DATA-SPECIFIC INFORMATION FOR: Data_Summary_SI.xlsx

This file summarizes the data shown in figures S1-S122 of the SI of the manuscript. A seperate sheet was set up for every relevant figure and labeled accordingly. Subfigures are seperated within a data sheet by a black bar.
The file contains obtained steady-state and transient UV-Vis and fluorescence spectrocopy data, computationally determined values, and other important data.
All data were collected in the laboratories of the authors. Please contact the corresponding authors directly if questions remain.

Sheet 1 (Fig. S1):
Emission spectra of the LEDs used in this work.
no abbreviations

Sheet 2 (Fig. S69):
a - Absorption spectra accompanying the E→Z isomerization of 22⊂H (20 μM) using a 365 nm LED
b - the subsequent Z→E isomerization using a 435 nm LED.
Abbreviations:
t = time; s = seconds

Sheet 3 (Fig. S71):
a - Absorption spectra accompanying the titration of (ps1)2⊂H (20 μM in water) with (E-2)2⊂H.
b - Absorption spectra accompanying the titration of (ps1)2⊂H (20 μM in water) with (E-7)2⊂H.
c - Heterodimer formation tendency followed by monitoring (E⋅ps1)⊂H’s absorbance at 509 nm.
no abbreviations

Sheet 4 (Fig. S72):
a - Changes in the fluorescence spectra of (ps1)2⊂H (20 μM in water) during titration with (E-9)2⊂H.
b - Time-resolved fluorescence spectra of (E-9⋅ps1)⊂H in water (λ_exc = 480 nm) (to maximize the molar fraction of ps1 within the heterodimer, 5 equiv. of (E-9)2⊂H with respect to (ps1)2⊂H were used).
c - Fluorescence decay traces of (E-9⋅ps1)⊂H (λ_em = 525 nm) compared to the fluorescence decays of (ps1)2⊂H at two different wavelengths (λ_em = 510 and 570 nm).
Abbreviations:
ns = nanoseconds; s = seconds; t = time

Sheet 5 (Fig. S74):
a - Changes in the absorption spectra of a 1:1 mixture of (ps1)2⊂H and (E-9)2⊂H (both 20 μM) pre-exposed to 525 nm light [i.e., (ps1)2⊂H + (Z-9)⊂H] during irradiation with blue light (435 nm).
b - One cycle of reversible switching of 9 (E→Z→E) by i) DESC in the presence of ps1 (525 nm) and the subsequent ii) direct photoisomerization using 435 nm light, followed by monitoring the absorbance at 334 nm (due to E-9) and 509 nm (due to ps1 within the (E-9⋅ps1)⊂H heterodimer).
c - Over 100 cycles of E⇄Z switching followed by absorption spectroscopy.
Abbreviations:
t = time; s = seconds

Sheet 6 (Fig. S75):
(A) Changes in the emission spectra (λ_exc = 490 nm) of a 1:1 mixture of (ps1)2⊂H and (E-9)2⊂H (both 20 μM) during green light (525 nm) irradiation.
(B) Subsequent irradiation with blue light (435 nm) affords E-9, shifting the equilibrium towards the heterodimer.
Abbreviations:
t = time; s = seconds

Sheet 7 (Fig. S76):
Effect of photosensitizer (ps1) loading on the kinetics of DESC (for E-9). 20 μM aqueous solutions of (E-9)2⊂H were exposed to green light (525 nm) in the presence of the following molar fractions of (ps1)2⊂H:
a - 50%;
b - 20%;
c - 10%;
d - 5%;
e - 0%
f - Changes in absorbance at 333 nm [i.e., (E-9)2⊂H’s wavelength of maximum absorption] over time in the presence of different fractions of (ps1)2⊂H.
Abbreviations:
t = time; s= seconds; min = minutes

Sheet 8 (Fig. S77):
(A) Changes in the absorption spectra of a 1:1 mixture of (ps1)2⊂H and (E-9)2⊂H (both 20 μM) upon irradiation with UV light (365 nm).
(B) Subsequent exposure to green light improves the PSS further.
Abbreviations:
t = time; s = seconds; min = minutes

Sheet 9(Fig. S78):
a - Changes in the absorption spectra of a 1:1 mixture of (ps1)2⊂H and (E-2)2⊂H (both 20 μM) during irradiation with green light (525 nm).
b - Changes in the absorption spectra of (E-2)2⊂H (20 μM) during irradiation with green light (525 nm).
c - Changes in the absorption spectra of (Z-2)⊂H (20 μM) [obtained by exposing (E-2)2⊂H to 365 nm light] during irradiation with green light (525 nm).
Abbreviations:
t = time; s = seconds; min = minutes

Sheet 10 (Fig. S79):
Decrease of absorbance of the E isomer (due to E→Z isomerization) of various azoarenes (20 μM solutions of E2⊂H in water) in the presence of 20 μM (ps1)2⊂H under green light irradiation (525 nm).
Abbreviations:
t = time; min = minutes

Sheet 11 (Fig. S80):
A sample of E-1 (20 μM) in CHCl3 was irradiated with 385 nm light until the PSS was reached. After adding 1 equiv. of TX, an absorption spectrum was recorded and irradiation was continued until a new PSS was reached.
no abbreviations

Sheet 12 (Fig. S81):
A UV-vis absorption spectrum of (TX)2⊂H in water.
no abbreviations

Sheet 13 (Fig. S82):
A sample of (E-1)2⊂H (20 μM) in CHCl3 was irradiated with 385 nm light until the PSS was reached. After the addition of 1 equiv. of (TX)2⊂H, an absorption spectrum was recorded and irradiation was continued until a new PSS was reached.
no abbreviation

Sheet 14 (Fig. S84):
a - Changes in the absorption spectra of (ps2)2⊂H (20 μM in water) during titration with (E-4)2⊂H.
b - Changes in the absorption spectra of (ps2)2⊂H (20 μM in water) during titration with (E-8)2⊂H.
c - Following E⋅ps2 heterodimer formation within host H by monitoring the absorbance of the heterodimer’s λ_max at 560 nm.
no abbreviations

Sheet 15 (Fig. S85):
Effect of photosensitizer ps2 loading on the kinetics of DESC (here, for E-4). 20 μM aqueous solutions of (E-4)2⊂H were exposed to yellow light (561 nm) in the presence of the following molar fractions of (ps2)2⊂H:
a - 50%;
b - 20%;
c - 10%;
d - 5%;
e - 1%;
f - 0%
g - Changes in absorbance at 354 nm [i.e., (E-4)2⊂H’s wavelength of maximum absorption] over time in the presence of different fractions of (ps2)2⊂H.
Abbreviations:
t = time; s = seconds; min = minutes

Sheet 16 (Fig. S86):
a - Following the back-isomerization (under 435 nm light) of (Z-4)⊂H, prepared by DESC of (E-4)2⊂H (in the presence of (ps2)2⊂H; both 20 μM).
b - One cycle of reversible switching of 4 (E→Z→E) by i) DESC in the presence of ps2 (561 nm) and the subsequent ii) direct photoisomerization using 435 nm light, followed by monitoring the absorbance at 352 nm (due to E-4) and 556 nm [due to ps2 within (E-4⋅ps2)⊂H].
c - Ten cycles of E⇄Z switching followed by absorption spectroscopy.
Abbreviations:
t = time; s = seconds; nm = nanometer

Sheet 17 (Fig. S87):
(A) Decrease of absorbance of the E isomer (due to E→Z isomerization) of various azoarenes (20 μM solutions of E2⊂H in water) in the presence of 20 μM (ps1)2⊂H under yellow light irradiation (561 nm).
(B) The E-9 outlier: No changes in the absorption spectra of (E-9)2⊂H in the presence of 1 equiv. of (ps2)2⊂H (both 20 μM) under yellow light irradiation.
Abbreviations:
t = time; s = seconds; min = minutes

Sheet 18 (Fig. S92):
a - Changes in the absorption spectra of (ps3)2⊂H (20 μM in water) during titration with (E-6)2⊂H.
b - Changes in the absorption spectra of (ps3)2⊂H (20 μM in water) during titration with (E-7)2⊂H.
c - Following E⋅ps3 heterodimer formation within host H by monitoring the absorbance of the heterodimer’s λmax at ~595 nm.
no abbreviations

Sheet 19 (Fig. S93):
Effect of ps3 loading on the kinetics of DESC (here, for E-1). 20 μM aqueous solutions of (E-1)2⊂H were exposed to orange light (599 nm) in the presence of the following molar fractions of (ps3)2⊂H:
a - 50%;
b - 20%;
c - 10%;
d - 5%;
e - 0%
f - Changes in absorbance at 320 nm [i.e., (E-1)2⊂H’s wavelength of maximum absorption] over time in the presence of different fractions of (ps3)2⊂H.
Abbreviations:
t = time; s = seconds

Sheet 20 (Fig. S94):
a - Following the back-isomerization (under 435 nm light) of (Z-1)⊂H, prepared by DESC of (E-1)2⊂H [in the presence of (ps3)2⊂H; both 20 μM].
b - One cycle of reversible switching of 1 (E→Z→E) by i) DESC in the presence of ps3 (599 nm) and the subsequent ii) direct photoisomerization using 435 nm light, followed by monitoring the absorbance at 319 nm (due to E-1) and 587 nm [due to ps3 within (E-1⋅ps3)⊂H].
c - Ten cycles of E⇄Z switching followed by absorption spectroscopy.
Abbreviations:
t = time; s = seconds; min = minutes; nm = nanometer

Sheet 21 (Fig. S95):
Decrease of absorbance of the E isomer (due to E→Z isomerization) of various azoarenes (20 μM solutions of E2⊂H in water) in the presence of 20 μM (ps3)2⊂H under orange light irradiation (599 nm).
Abbreviations:
t = time; min = minutes

Sheet 22 (Fig. S96):
a - Changes in the absorption spectra of (ps4)2⊂H (20 μM in water) during titration with (E-6)2⊂H.
b - Changes in the absorption spectra of (ps4)2⊂H (20 μM in water) during titration with (E-7)2⊂H.
c - Following E⋅ps4 heterodimer formation within host H by monitoring the absorbance of the heterodimer’s λ_max at ~625 nm.
no abbreviations

Sheet 23 (Fig. S97):
a - Effect of red light (635 nm) irradiation on the absorption spectra of E-3 (20 μM in water) in the absence of ps4 and H.
b - Effect of red light (635 nm) irradiation on the absorption spectra of E-3 (20 μM in water) in the presence of 20 μM ps4 but in the absence of H.
c - Effect of red light (635 nm) irradiation on the absorption spectra of E-3 (20 μM in water) in the presence of both ps4 and H (both 20 μM).
Abbreviations:
t = time

Sheet 24 (Fig. S98):
Effect of ps4 loading on the kinetics of DESC (here, for E-2). 20 μM aqueous solutions of (E-2)2⊂H were exposed to red light (635 nm) in the presence of the following molar fractions of (ps4)2⊂H:
a - 50%;
b - 20%;
c - 10%;
d - 5%;
e - 1%;
f - 0%
g - Changes in absorbance at 354 nm [i.e., (E-2)2⊂H’s wavelength of maximum absorption] over time in the presence of different fractions of (ps4)2⊂H.
Abbreviations:
t = time; s = seconds; min = minutes

Sheet 25 (Fig. S99):
a - Following the back-isomerization (under 435 nm light) of (Z-2)⊂H, prepared by DESC of (E-2)2⊂H [in the presence of (ps4)2⊂H; both 20 μM].
b - One cycle of reversible switching of 1 (E→Z→E) by i) DESC in the presence of ps4 (635 nm) and the subsequent ii) direct photoisomerization using 435 nm light, followed by monitoring the absorbance at 354 nm (due to E-2) and 618 nm [due to ps4 within (E-2⋅ps4)⊂H].
c - Ten cycles of E⇄Z switching followed by absorption spectroscopy.
Abbreviations:
t = time; s = seconds; nm = nanometer

Sheet 26 (Fig. S100):
Decrease of absorbance of the E isomer (due to E→Z isomerization) of various azoarenes (20 μM solutions of E2⊂H in water) in the presence of 20 μM (ps4)2⊂H under red light irradiation (635 nm).
Abbreviations:
t = time; min = minutes

Sheet 27 (Fig. S102):
a - A series of UV-vis absorption spectra of E-3/Z-3 mixtures whose composition had been determined by NMR spectroscopy.
b - The resulting calibration curve can be used for determining the PSS directly from absorption spectra.
no abbreviations

Sheet 28 (Fig. S103):
a - UV-vis absorption spectra of (ps4)2⊂H before after the addition of increasing amounts of free Z-2 (numbers of equivalents with respect to the host).
b - UV-vis absorption spectra of (Z-2)⊂H before after the addition of increasing amounts of ps4 (numbers of equivalents with respect to the host).
Abbreviations:
t = time

Sheet 29 (Fig. S104):
a - A series of UV-vis spectra of a mixture of (ps2)2⊂H and 5 exposed to yellow light (561 nm).
b - Irradiating a mixture of (ps2)2⊂H and 3 with yellow light (561 nm) under the same conditions results in fast and near-quantitative isomerization.
c - Subtracting the spectra of the PSS of (B) from the one shown in Fig. 5C proves that 5 remains in the E-state while 3 isomerizes.
Abbreviations:
t = time; s = seconds

Sheet 30 (Fig. S105):
No changes in the absorption spectra of the E-1 + ps4 mixture upon irradiation with red light (635 nm) in the presence of the following hosts:
a - γ-CD;
b - CB[8];
c - the tripyridine-based Fujita cage
Abbreviations:
t = time

Sheet 31 (Fig. S106):
An attempt to induce photosensitization using the Pd precursor instead of host H
Abbreviations:
t = time

Sheet 32 (Fig. S107):
Abbreviations:
Evolution of the absorption spectra of a 2:2:1 mixture of 3, ps4, and host H under red light (625 nm) irradiation in
a - water;
b - 10 vol% DMSO in water;
c - 20 vol% DMSO in water;
d - 30 vol% DMSO in water;
e - 40 vol% DMSO in water;
f - 50 vol% DMSO in water.
g - Comparison of the absorption spectra of the resulting photostationary states.
t = time; s = seconds

Sheet 33 (Fig. S108):
Saturation curve of (E-9⋅ps1)⊂H [the sample was prepared by mixing (ps1)2⊂H with (E-9)2⊂H in a 1:5 ratio].
Abbreviations:
t = time; s= seconds

Sheet 34 (Fig. S109):
Absorption spectra of 80 μM (ps1)2⊂H and a 1:2 mixture of (ps1)2⊂H with (E-9)2⊂H in water used for fs-TAS measurements.
Abbreviations:
TAS = transient absorption spectroscopy

Sheet 35 (Fig. S110):
a - A 2D fs-TA spectrum of (ps1)2⊂H (80 μM in water) represented as a color map (λ_exc = 500 nm).
b - A 2D fs-TA spectrum of (ps1)2⊂H (80 μM in water) represented as four-exponential fits to the experimental decays with the associated residuals (λ_exc = 500 nm).
c - A 2D fs-TA spectrum of a 1:2 mixture of (ps1)2⊂H and (E-9)2⊂H [i.e., predominantly (E-9⋅ps1)⊂H] represented as a color map (λ_exc = 510 nm).
d - A 2D fs-TA spectrum of a 1:2 mixture of (ps1)2⊂H and (E-9)2⊂H represented as four-exponential fits to the experimental decays with the associated residuals (λ_exc = 510 nm).
no abbreviations

Sheet 36 (Fig. S111):
a - fs-TA spectra of (ps1)2⊂H (80 μM in water) at selected delay times (λ_exc = 500 nm).
b - The corresponding decay component spectra from four-exponential global fitting.
c - Absorption changes of (ps1)2⊂H at 412 and 429 nm.
d - fs-TA spectra for the 1:2 mixture of (ps1)2⊂H and (E-9)2⊂H [i.e., predominantly (E-9⋅ps1)⊂H] at selected delay times (λ_exc = 510 nm).
e - The corresponding decay component spectra from four-exponential global fitting.
f - Absorption changes of ps1 within (E-9⋅ps1)⊂H at 412 and 429 nm.
Abbreviations:
a - bodipy-0.1-ps = absorption difference after 0.1 picoseconds (data); bodipy-0.1-fit = absorption difference after 0.1 picoseconds (fit); bodipy-1-ps = absorption difference after 1 picosecond (data); bodipy-1-fit = absorption difference after 1 picosecond (fit); bodipy-50-ps = absorption difference after 50 picoseconds (data); bodipy-50-fit = absorption difference after 50 picoseconds (fit); bodipy-500-ps = absorption difference after 500 picoseconds (data); bodipy-500-fit = absorption difference after 500 picoseconds (fit); bodipy-5000-ps = absorption difference after 5000 picoseconds (data); bodipy-5000-fit = absorption difference after 5000 picoseconds (fit);
b - bodipy-exp1(0.206+-0.001) = decay component spectra from first exponent of fit; bodipy-exp2(14.6+-0.3) = decay component spectra from second exponent of fit; bodipy-exp3(1302+-16) = decay component spectra from third exponent of fit; bodipy-exp4(over-60ns) = decay component spectra from fourth exponent of fit
c - no abbreviations
d - [analogous to a]
e - [analogous to b]
f - no abbreviations

Sheet 37 (Fig. S112):
Absorption changes at 483 nm associated with the ground-state bleaching of ps1 (raw data with four-exponential fits).
no abbreviations

Sheet 38 (Fig. S113):
Absorption spectra of 30 μM aqueous solutions of (ps1)2⊂H without and with different fractions of (E-9)2⊂H used for μs-TAS experiments.
Abbreviations:
abs-bodipy_15ul-4mM-in-2ml-H2O = absorption of encapsulated ps1 without encapsulated E-9; abs-r0.3 = absorption of encapsulated ps1 with 0.33 equivalent encapsulated E-9; abs-r1 = absorption of encapsulated ps1 with 1 equivalent encapsulated E-9

Sheet 39 (Fig. S114):
a - μs-TA decays of (ps1)2⊂H (30 μM in water) under ambient conditions and N2 purging, monitored at 430 nm after 510 nm excitation, averaging 1000 pulses under continuous pulsed excitation.
b - μs-TA decay of the same solution under N2 purging for 10 min.
no abbreviations

Sheet 40 (Fig. S115):
a - μs-TA decays of unpurged (ps1)2⊂H (30 μM in water) at 430, 350, and 470 nm. The decays were measured using 510 nm excitation, averaging 1000 pulses under continuous pulsed excitation.
b - μs-TA decays of unpurged (ps1)2⊂H (30 μM in water) in the presence of 0.33 equiv. (E-9)2⊂H.
c - μs-TA decays of unpurged (ps1)2⊂H (30 μM in water) in the presence of 1 equiv. (E-9)2⊂H.
d,e - μs-TA decay component spectra of (ps1)2⊂H [free and in the presence of (E-9)2⊂H] and from global biexponential fitting.
f - Absorption spectra of pristine (ps1)2⊂H and 1:1 mixture of (ps1)2⊂H and (E-9)2⊂H in water before and after μs-TAS measurements.
Abbreviations:
d - r0 16.9(0.5)us = decay component spectra from first exponent of fit; r0.3 17.5(0.7)us = decay component spectra from second exponent of fit; r1 16.1(0.6)us = decay component spectra from third exponent of fit
e - [analogus to d]
f - abs-bodipy-15ul-4mM-in-2ml = absorption of encapsulated ps1 without encapsulated E-9; abs-r1 = absorption of encapsulated ps1 with 1 equivalent encapsulated E-9; abs-r1_afterTAS = absorption of encapsulated ps1 with 1 equivalent encapsulated E-9 after transient absorption spectroscopy measurement

Sheet 41 (Fig. S116):
The energy diagrams for free ps1, heterodimer (E-1)⋅ps1, and free E-1.
no abbreviations

Sheet 42 (Fig. S117):
The energy diagrams for free ps2, heterodimer (E-1)⋅ps2, and free E-1.
no abbreviations

Sheet 43 (Fig. S118):
The energy diagrams for free ps1, heterodimer (E-9)⋅ps1, and free E-9.
no abbreviations

Sheet 44 (Fig. S119):
The energy diagrams for free ps2, heterodimer (E-9)⋅ps2, and free E-1.
no abbreviations

Sheet 45 (Fig. S121):
b - Quantifying host flexibility by monitoring the distance between the two axial Pd centers in two inclusion complexes, (E-1⋅ps1)⊂H and (E-9⋅ps2)⊂H.
c - Variation of E-1’s and E-9’s C–N=N–C dihedral angle Φ within (E-1⋅ps1)⊂H and (E-9⋅ps2)⊂H, respectively, over the course of the trajectories.
Abbreviations:
t = time; ps= picoseconds

Sheet 46 (Fig. S122):
Relaxed surface scans along the C–N=N–C dihedral angle Φ in:
a - azobenzene 1 within the 1⋅ps1 heterodimer;
b - azobispyrazole 9 within the 9⋅ps1 heterodimer;
c - azobenzene 1 within the 1⋅ps2 heterodimer;
d - azobispyrazole 9 within the 9⋅ps2 heterodimer.
Abbreviations:
eV = electron volt