DOI: 10.5061/dryad.4qrfj6qg1
title: Disequilibrating azobenzenes by visible-light sensitization under confinement

description: The ability to photoswitch azobenzenes from their stable E isomer to the
 metastable Z state is the basis of numerous applications of these
 molecules. However, this reaction typically requires UV light, which
 limits the applicability, particularly in biological settings. Here we
 introduce DisEquilibration by Sensitization under Confinement (DESC), a
 biomimetic approach to switch various azobenzenes using visible light of
 desired color, including red. DESC relies on a combination of a
 macrocyclic host and a photosensitizer, which act together to bind and
 selectively sensitize E-azobenzenes. After switching to the Z isomer, the
 azobenzene loses its affinity to—and is expelled from—the host, which can
 convert additional copies of E into Z. In this way, the
 host/photosensitizer complex acts as a light-driven supramolecular
 machine, converting photon energy into chemical energy in the form of
 out-of-equilibrium photostationary states, including ones that cannot be
 accessed via direct photoexcitation.
description: 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 3. Links to other publicly
 accessible locations of the data: None 4. Links/relationships to ancillary
 data sets: None 5. Was data derived from another source? No A. If yes,
 list source(s): NA 6. 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 2.
 Relationship between files, if important: None 3. Additional related data
 collected that was not included in the current data package: None 4. 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
 #########################################################################
 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
 #########################################################################
 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