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. 2026 Oct 19. Online ahead of print. doi: 10.1039/d6py00788k

Accessing block copolymers with independently modulated tacticities using sequential cationic–anionic polymerization of vinyl ethers and thiiranes

William Ramos a, Nicholas M Legaux b, Brandon M Hosford a, Hanlin M Wang c, Elizabeth A Murphy c, Alicia C Huggett a, Frank A Leibfarth b, Jessica R Lamb a,✉
PMCID: PMC13682421  PMID: 42903849

Abstract

Tacticity can have profound effects on the physical properties of polymers, such as self-assembly of block copolymers (BCPs). Despite its promise, previous reports on changing tacticity of BCPs have primarily focused on changing a single block or comparing fully isotactic to fully atactic copolymers. Herein, we report a platform to easily access fully atactic, fully isotactic, and mixed tacticity poly(vinyl ether)-block-poly(thiirane) BCPs. Isotacticity was independently accessed via stereoselective polymerization of vinyl ethers and by using enantiopure thiirane monomers, respectively. Thermal analyses of these materials were performed and semi-crystallinity was observed in aryl-containing isotactic blocks. For BCPs with alkyl side chains or atactic aryl side chains, fractionation on the basis of composition was performed to accelerate self-assembly studies. These fractionated BCPs were characterized via small-angle X-ray scattering (SAXS), where we observed hexagonally-packed cylinder or lamellar morphologies for some fractions. The development of this framework of selective tacticity modulation opens up facile access to diverse BCPs with varying thermal, solution-state, and bulk properties.

Multi-monomer class block copolymers with systematically varied block tacticity were accessed via (1) non-selective/stereoselective cationic polymerization and (2) racemic/enantiopure monomers.graphic file with name d6py00788k-ga.webp

Introduction

The tacticity (i.e., the relative stereochemistry of adjacent stereogenic centers1) of polymer chains can have a profound influence on their thermal,2–4 rheological,5–10 mechanical,11 and barrier properties.12–14 In particular, tacticity is known to impact semi-crystallinity12 and self-assembly of block copolymers (BCPs);15–19 however, tacticity is infrequently leveraged as a deliberate structural handle owing to the synthetic challenges of stereocontrol. The synthesis of chemically diverse BCPs with independent control of each blocks’ stereochemistry would provide a unique opportunity to systematically investigate the role of tacticity on BCP morphology and properties because most studies in this field are limited to changing tacticity of a single block (Fig. 1A)16,19–22 or comparing a fully isotactic BCP with a fully atactic BCP.23

Fig. 1. Previous work on changing tacticity of (A) a single block and (B) single monomer class BCPs. (C) Known stereoselective cationic polymerization of VEs. (D) Sequential (stereoselective) cationic polymerization of VEs and TAGT of racemic/enantiopure thiiranes to access systematically varied tacticities of multi-monomer-class BCPs.

Fig. 1

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To our knowledge, there is only a single systematic report that individually modulates the block tacticity of a diblock copolymer (Fig. 1B),24 but both blocks are based on glycidyl ether monomers, limiting the explored chemical space to variable side chains with a structurally uniform backbone. Understanding structure–morphology–property relationships in an expanded chemical space will require systematic studies on more diverse BCPs synthesized from chemically distinct monomer classes.

Disparate monomer classes often require different polymerization mechanisms, which can be combined in a straightforward manner through a “universal mediator” approach. Thiocarbonyl thio compounds (TCTs) are common universal mediators for multi-mechanism BCPs,25–36 including poly(vinyl ether)-block-poly(thiirane)s from sequential cationic polymerization and thioacyl anionic group transfer polymerization (TAGT).37,38 To date, only the fully atactic versions of these BCPs have been reported; however, the isotactic variants of each homopolymer are known. Isotactic poly(vinyl ether)s (pVEs) can be accessed through stereoselective cationic polymerization using chiral Brønsted or Lewis acids (Fig. 1C),39–46 which can be compatible with TCT mediators.41,47,48 Isotactic poly(thiirane)s without a TCT mediator have been reported via an enantiopure feedstock or stereoselective polymerizations;49–53 however, the use of an enantiopure thiirane monomer in TAGT has not been reported.

Herein, we use a TCT universal mediator to combine cationic polymerization of vinyl ethers (VEs) and TAGT of thiiranes to access a systematic library of fully atactic, fully isotactic, and mixed tacticity BCPs (Fig. 1D). Isotacticity was introduced to (1) the pVE block via stereoselective cationic polymerization using a chiral Brønsted acid and (2) the poly(thiirane) block via an enantiopure thiirane monomer. Characterization of the BCPs with nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) demonstrated successful chain extensions and thermal properties expected from each block. Finally, we studied the effect of tacticity on BCP self-assembly. To streamline our synthetic workflow, we used automated column chromatography to fractionate several parent polymers on the basis of composition to rapidly generate a series of diverse fractions that were analyzed via small-angle X-ray scattering (SAXS).54–58 We found that the identity of the side chains and the tacticity of the blocks affected the BCPs’ ability to fractionate into samples with narrow composition and found the preliminary composition window where ordered morphologies were observed.

Results and discussion

Synthesis of atactic and isotactic homopolymers

We first sought to optimize the syntheses of the atactic and isotactic homopolymers. In this work, all atactic polymers/blocks are labelled with the prefix “a-” and all isotactic polymers/blocks are labelled with the prefix “iso-”. For the cationic polymerizations, poly(ethyl vinyl ether) [p(EVE)], poly(benzyl vinyl ether) [p(BnVE)], and poly(isobutyl vinyl ether) [p(IBVE)] were selected as readily available and well-studied substrates for cationic polymerizations.26,39–41,59,60 To synthesize atactic poly(vinyl ether)s, previously reported methods of either photocontrolled cationic polymerization (photo-CP)37,59,61 or reversible deactivation cationic polymerization (RDCP)38,62 were performed using ethyl 1-(2-methylpropoxy)ethyl carbonotrithiolate (TCT1) as the mediator (see section SII.A).

To access isotactic poly(vinyl ether)s, stereoselective cationic polymerizations of BnVE and IBVE were explored using imidodiphosphorimidate (IDPi) Brønsted acid catalysts and TCT1 as a chain-transfer agent (CTA). Similar to previous reports with related catalysts,41,47 we included toluene as a cosolvent in order to solubilize TCT1. The polymerizations were quenched with sodium ethyl trithiocarbonate to ensure good chain end fidelity for sequential anionic chain-extension.38,62 For both monomers, the addition of TCT1 to the stereoselective polymerization resulted in polymers with lower number-average molar masses (Mn = 16.0–20.2 kDa) and comparable dispersities (Đ = 1.84–1.85) while maintaining excellent isotacticities [>88% meso diads (% m)] (Table 1, see section SII.B.1). The fact that TCT1 did not significantly decrease dispersity suggests that the rate of chain transfer is slow,26,61,63,64 likely due to the IDPi catalyst closely coordinating with the active chain end.

Table 1. Adding TCT1 to the stereoselective cationic polymerization of VEs using IDPi catalystsa.

graphic file with name d6py00788k-u1.webp
Entry VE Solvent TCT1 (eq.) M n b (kDa) Đ b Tacticityc
1 BnVE PhMe 0 107 1.73 89% m
2 BnVE PhMe 1 16.0 1.84 88% m
3 IBVE MeCy 0 302 1.96 90% m
4 IBVE 1 : 1 MeCy : PhMe 1 20.2 1.85 88% m
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a

Standard conditions: VE (100 eq.), TCT1 (0–1 eq.), IDPi (0.1 mol%, rel. to VE), solvent (100 mM), −78 °C, 1 h. IDPi1 used for BnVE, IDPi2 used for IBVE.

b

Determined via TOSOH SEC in THF calibrated against poly(styrene) standards.

c

Determined via13C NMR spectroscopy.

We verified that both the atactic and isotactic poly(thiirane)s can be made using the same TAGT conditions using racemic [i.e., 3-phenoxypropylene sulfide (POPS) and propylene sulfide (PS)] and enantiopure (i.e., (S)-POPS and (S)-PS) monomers, respectively. Both thiirane monomers were synthesized from the appropriate epoxide precursors and potassium thiocyanate. Note that converting the epoxide to the thiirane inverts the stereochemistry of the three-membered heterocycle via an SN2 reaction at the stereogenic center (see Fig. S7 for the full mechanism).

The poly(thiirane)s were synthesized with TCT1 as the mediator and tetraphenylphosphonium chloride as the catalyst via TAGT in 15 mM dimethylacetamide (DMAc). Both (rac)-POPS and (S)-POPS (50 : 1 [thiirane] : [TCT1]) were polymerized with high conversions (72–81%) and good agreement between Mn,theo and Mn with moderate Đ (1.39–1.56; Table 2, entries 1 and 2). Similarly, homopolymerization of (rac)-PS and (S)-PS (200 : 1 [thiirane] : [TCT1]) had high conversions (>96%), controlled Mn, and low Đ (1.20–1.29; Table 2, entries 3 and 4). The isotacticities of the poly(thiirane)s corresponded to the enantiopurities of the monomers, confirming stereoretentive polymerization (Fig. S9) and leading to >93% m compared to 42–54% m for the atactic variants (see section SII.B.1).

Table 2. Synthesis of atactic and isotactic poly(thiirane)sa.

graphic file with name d6py00788k-u2.webp
Entry Thiirane Conv.b M n,theo b (kDa) M n c (kDa) Đ c Tacticityd
1 (rac)-POPS 81% 7.27 8.33 1.39 54% m
2 (S)-POPS 72% 6.71 8.06 1.56 >99% m
3 (rac)-PS 96% 14.5 15.7 1.29 42% m
4 (S)-PS >99% 15.1 14.6 1.20 93% m
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a

Standard conditions for POPS: 50 : 1 [POPS] : [TCT1], Ph4PCl (0.33 eq.), DMAc (15 mM), 60 °C, 6 h. Standard conditions for PS: 200 : 1 [PS] : [TCT1], Ph4PCl (0.33 eq.), DMAc (15 mM), 60 °C, 3 h.

b

Determined via1H NMR spectroscopy of the crude reaction mixture.

c

Entries 1 and 2: determined via SEC in DMF calibrated against poly(methyl methacrylate) standards. Entries 3 and 4: determined via Waters SEC in THF calibrated against poly(styrene) standards.

d

Determined via13C NMR spectroscopy.

BCP formation

With the ability to vary tacticity of each block, we moved on to BCP formation. All polyVE homopolymers containing the TCT chain-end were chain-extended using TAGT to yield BCPs (Table 3 and Fig. S17–S23). First, a-p(EVE) was chain-extended with (rac)-POPS and (S)-POPS (entries 1 and 2) under the standard TAGT conditions described above. The other pVEs [e.g., p(IBVE) and p(BnVE)] are insoluble in DMAc or NMP, the typical solvents for TAGT. Therefore, we used 2 : 1 DMAc : THF as the solvent system for the chain extensions, as we previously found that THF can be used as a cosolvent to successfully solvate pVEs.38 Additionally, the isotactic pVEs were poorly soluble in this co-solvent mixture at our typical concentration of 15 mM; thus, the concentration was decreased to 5 mM for the chain extensions of p(BnVE) and p(IBVE) (see section SIII.C).

Table 3. Chain extensions of atactic and isotactic pVEs with racemic and enantiopure thiiranes to generate BCPs with varying tacticitiesa.

graphic file with name d6py00788k-u3.webp
Entry BCP Monomer Conv.g M n h (kDa) Đ h T o i (°C) T g j (°C) T m j (°C)
1b a-p(EVE)-b-a-p(POPS) (rac)-POPS 76% 10.1 1.38 271, 373l −30, 18l —
2c a-p(EVE)-b-iso-p(POPS) (S)-POPS 67% 11.3 1.42 290, 382 −32, 20 118k
3d iso-p(BnVE)-b-iso-p(PS) (S)-PS 85% 16.2 1.41 284, 441 −30, −5 151
4e a-p(IBVE)-b-a-p(PS) (rac)-PS 36% 23.2 1.41 295, 398 −40, −18 —
5e a-p(IBVE)-b-iso-p(PS) (S)-PS 37% 22.5 1.40 298, 397 −38, −14 —
6f iso-p(IBVE)-b-a-p(PS) (rac)-PS 84% 41.3 1.29 298, 388 −39, −17 141
7f iso-p(IBVE)-b-iso-p(PS) (S)-PS >99% 43.7 1.36 294, 406 −38, −17 138
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a

Standard conditions: thiirane (50–200 eq.), pVE (1 eq.), Ph4PCl (0.33 eq.), solvent, 60 °C, 6 h.

b

Starting a-p(EVE): Mn = 3.38 kDa, Đ = 1.33 (Table S1, entry 1). Used 50 eq. (rac)-POPS, 15 mM DMAc as solvent.

c

Starting a-p(EVE), Mn = 4.30 kDa, Đ = 1.31 (Table S1, entry 2). Used 50 eq. (S)-POPS, 15 mM DMAc as solvent.

d

Starting iso-p(BnVE), Mn = 7.71 kDa, Đ = 1.95 (Table S2, entry 3). Used 50 eq. (S)-PS, 5 mM 2 : 1 DMAc : THF as solvent.

e

Starting a-p(IBVE), Mn = 14.2 kDa, Đ = 1.27 (Table S1, entry 2). Used 200 eq. (rac)-PS, 5 mM 2 : 1 DMAc : THF as solvent.

f

Starting iso-p(IBVE), Mn = 19.8 kDa, Đ = 1.89 (Table S2, entry 5). Used 200 eq. (S)-PS, 5 mM 2 : 1 DMAc : THF as solvent.

g

Determined via1H NMR spectroscopy of the crude reaction mixture.

h

Entries 1 and 2: determined via SEC in DMF with 0.025 M LiBr calibrated against poly(methyl methacrylate) standards. Entries 3–7: determined via Waters SEC in THF calibrated against poly(styrene) standards.

i

Calculated from TGA thermograms.

j

Determined by DSC using the 2nd heat.

k

Determined by DSC using the 1st heat.

l

Previously reported.37

Using these optimized conditions, we generated iso-p(BnVE)-b-iso-(PS) (Table 3, entry 3) and the full set of tacticities for p(IBVE)-b-p(PS): fully atactic, fully isotactic, and mixed tacticities (entries 4–7). We observed moderate conversions (36–37%) and clean shifts in the SEC traces when chain extending from atactic pVEs (Fig. 2A & Fig. S20, S21); whereas, chain extending from isotactic pVEs resulted in higher conversions (84–99%) but sometimes displayed minor low molar mass tailing (Fig. S19 and S22–S26).

Fig. 2. (A) Representative SEC traces showing chain extension of a-p(IBVE) to a-p(IBVE)-b-a-p(PS). (B) Representative DSC thermograms of p(IBVE)-b-p(PS) with varying tacticities (Tg and Tm corresponding to p(IBVE) (blue) and p(PS) (red) are marked); data shown are taken from the second heating cycles at a scan rate of 10 °C min−1.

Fig. 2

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Thermal properties

We then investigated the thermal properties of the BCPs with varied tacticities. TGA thermograms were collected and the extrapolated onset temperatures of degradation (Tos) were calculated (see section SII.D). As expected, all BCPs underwent two mass loss events regardless of the block tacticity: To = 271–298 °C and 373–406 °C, corresponding to the p(thiirane) and pVE blocks, respectively.

DSC thermograms for each BCP revealed two glass transition temperature (Tg) features that closely match their respective homopolymers: −40 to −30 °C corresponding to the pVE blocks and −18 to 20 °C corresponding to the p(thiirane) blocks (Fig. 2B, see section SII.D). The tacticity of each block did not affect the Tg values. We observe a melting temperature (Tm) for BCPs that contain iso-pVE and iso-p(POPS) that is not present in their atactic analogues. Further evidence for semi-crystallinity of these polymers is that their physical appearances are more solid-like compared to the tacky forms of the remaining BCPs.

Effect of tacticity on fractionation and self-assembly

To further study the effects of tacticity on these BCPs, we explored the fractionation of the parent polymers on the basis of composition using automated column chromatography—an established method to generate a library of polymers from relatively few synthetic batches.54–58 This fractionation occurs when different polymer chains in the parent sample have different affinities for the stationary and mobile phases such that the sample separates into constituents with varying polarities (i.e., composition).54 In addition to affinity, fractionation on the basis of size is also possible; however, size is typically not the main mechanism of separation and the magnitude of this effect can be determined via SEC pre- and post-fractionation.55,65 Thin-layer chromatography (TLC) is first performed to identify a suitable mobile phase, indicated by the presence of streaking.55 In some cases, a suitable chromatographic system cannot be found, resulting in column “breakthrough” in which the parent polymer elutes with the solvent front with little to no separation due to insufficient interactions with the stationary phase.

When performing TLC on our BCPs, we observed streaking for a-p(EVE)-b-a-p(POPS) and all four p(IBVE)-b-p(PS) BCPs using ethyl acetate/hexanes as the solvent system. However, BCPs containing isotactic aryl side chains [i.e., iso-p(BnVE) and iso-p(POPS)] exhibited breakthrough on TLC in a variety of solvent mixtures containing ethyl acetate, hexanes, acetone, dichloromethane, and methanol (Fig. 3A). We hypothesize that the breakthrough is due to the stereoregular aromatic side chains associating intramolecularly resulting in fewer intermolecular interactions with the stationary phase. Future work on exploring the origin of the breakthrough and compatibilizing the BCPs to be amenable to fractionation is underway. Due to these issues, the self-assembly of BCPs containing isotactic aryl side chains was not further explored.

Fig. 3. (A) Fractionation workflow with polymer either undergoing column breakthrough (BCPs with isotactic aryl side chains) or fractionation on the basis of composition (remaining BCPs). (B) Representative composition graph and fraction mass of child polymers from parent a-p(IBVE)-b-a-p(PS).

Fig. 3

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Following fractionation, samples of similar block composition were combined, dried, annealed, and analyzed via small-angle X-ray scattering (SAXS) to determine the morphology of the fractionated samples. For a-p(EVE)-b-a-p(POPS), most samples were disordered, but some self-assembled into lamellar (LAM) or hexagonally-packed cylinder (HEX) morphologies (see section SII.E.1). Some samples appeared to be poorly ordered with unknown morphologies (UNK). The LAM phase was observed when the mol% of p(EVE) was 50–70% and the HEX phase was observed when the mol% of p(EVE) was 46–47%. Note that the parent BCP formed a poorly ordered HEX phase prior to fractionation; however, fractionation resulted in the formation of more well-defined morphologies (Fig. S52).

For the full set of p(IBVE)-b-p(PS) BCPs, we were able to fractionate the parent polymers on the basis of composition, with varying levels of column breakthrough (see section SII.E.2). The tacticity of the blocks impacted the fractionation profile, such that a-p(IBVE)- and iso-p(IBVE)-containing BCPs resulted in child polymers with 32–100 and 24–68 mol% VE block, respectively (Fig. 3B & Fig. S53, S55, S57, S58). The presence of 100 mol% pVE indicated that a portion of the p(IBVE) homopolymer did not successfully chain extend, but the fact that this fraction separated from the BCP-containing fractions demonstrates this homopolymer impurity was removed. SEC analyses were performed on some fractions with sufficient mass, showing similar molar mass distributions compared with the parent BCP (Fig. S54 and S56).

The polymers containing the a-p(IBVE) blocks were annealed at 70 °C for 18 h while the polymers containing the iso-p(IBVE) blocks were annealed at 160 °C (well above the Tg and Tm) for 20 h. About half of the a-p(IBVE) BCP fractions had low sample volume, resulting in low signal; however, for a-p(IBVE)-b-a-p(PS), the HEX phase was observed for fractions containing 58–63 mol% p(IBVE) (Fig. 4 and Fig. S59). For a-p(IBVE)-b-iso-p(PS), the observed self-assembly window was extended to 56–77 mol% p(IBVE) (Fig. 4 and Fig. S60). These preliminary data suggest that the addition of isotacticity expanded the compositional space of self-assembly; however, more work with larger amounts of parent polymers is needed to confirm this trend. Unfortunately, the low sample volume for polymers containing iso-p(IBVE) resulted in low signal, which made it difficult to visualize higher-order Bragg reflections. Future work in optimizing annealing conditions (e.g. solvent casting) to achieve higher order and performing fractionation with a higher loading of parent BCP is ongoing.

Fig. 4. (A) Composition and morphology of a-p(IBVE)-b-a-p(PS) and a-p(IBVE)-b-iso-p(PS). (B) Representative SAXS traces of child polymers from parent a-p(IBVE)-b-a-p(PS), where allowed reflections are indexed on each trace. HEX = hexagonally packed cylinders, UNK = unknown/poorly ordered morphology.

Fig. 4

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Conclusions

In summary, we identified and demonstrated pVE-b-p(thiirane) as a platform to easily access fully atactic, fully isotactic, and mixed tacticity BCPs with a variety of vinyl ether and thiirane monomers. Isotacticity was independently introduced via stereoselective cationic polymerization of VEs and/or by using enantiopure thiirane monomers. The thermal properties of these materials were determined using TGA and DSC, and semi-crystallinity was observed for BCPs containing iso-pVE and iso-p(POPS). The effect of block tacticity was notable in the fractionation on the basis of composition where BCPs with isotactic aryl side chains exhibited column breakthrough, resulting in the inability to adsorb to the stationary phase. Conversely, BCPs with alkyl or atactic aryl side chains were fractionated, annealed, and characterized using SAXS. Despite many fractions having low signal due to low sample mass, we observed HEX, LAM, and additional poorly ordered morphologies. The composition window in which self-assembly was observed appeared to be influenced by the tacticity of the poly(thiirane) block, though further investigations are necessary with larger sample masses and further development of sample preparation conditions. This platform demonstrates how the universal mediator approach can translate well-developed synthetic methods that yield stereoregular homopolymers to access multi-monomer class BCPs with independently controlled block tacticities. This control enables systematic investigation into the effect of tacticity on thermal, solution-state, and bulk properties.

Author contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Credit: William Ramos: conceptualization, data curation, formal analysis, investigation, methodology, validation, visualization, writing – original draft, and writing – review and editing; Nicholas M. Legaux: data curation, formal analysis, investigation, methodology, writing – original draft, and writing – review & editing; Brandon M. Hosford: conceptualization, data curation, formal analysis, investigation, methodology, visualization, and writing – original draft; Hanlin M. Wang: data curation, formal analysis, investigation, and methodology; Elizabeth A. Murphy: data curation, formal analysis, investigation, methodology, and visualization; Alicia C. Huggett: formal analysis, visualization, writing – review & editing; Frank A. Leibfarth: formal analysis, funding acquisition, resources, writing – original draft, and writing – review & editing; Jessica R. Lamb: conceptualization, formal analysis, funding acquisition, project administration, resources, supervision, writing – original draft, and writing – review & editing.

Conflicts of interest

There are no conflicts to declare.

Supplementary Material

PY-OLF-D6PY00788K-s001

Acknowledgments

This work was supported by the University of Minnesota (UMN), the McKnight Land-Grant Professorship (JRL), the Camille and Henry Dreyfus Foundation (TC-26-031). The research reported here was partially supported by the BioPACIFIC Materials Innovation Platform of the National Science Foundation (NSF) under Award No. DMR-1933487 and DMR-2445868 (equipment and characterization). W. R. was partially supported by the 3M Science and Technology Graduate Fellowship and the UMN Graduate School Research Travel Request. N. M. L. and F. A. L. acknowledge the National Institute of General Medical Sciences of the National Institute of Health (NIH) under Award Number 1-R35-GM142666. B. M. H. was partially supported by the Lester C. and Joan M. Krogh Excellence Fellowship and the 2025–26 Doctoral Dissertation Fellowship (DDF) from the University of Minnesota Graduate School. NMR analyses that were performed at the UMN Department of Chemistry Nuclear Magnetic Resonance Laboratory which is supported by the Research and Innovation Office (RIO), College of Science and Engineering (CSE), the Department of Chemistry at UMN, and the Office of the Director, NIH (S10OD011952). Part of this work was carried out in the CSE Polymer Processing and Characterization Facility at UMN, which has received capital equipment funding from the NSF through UMN Materials Research Science and Engineering Center (MRSEC) (DMR-2011401). The content of this paper is the sole reasonability of the official views or the endorsement by the NSF or NIH. The authors would like to thank Prof. Timothy Lodge for helpful discussions.

Data availability

The data supporting this article has been included as part of the supplementary information (SI). Supplementary information: supplemental data, experimental details, characterization data, and supporting figures and tables. See DOI: https://doi.org/10.1039/d6py00788k.

The primary data files are archived with the Data Repository for the University of Minnesota (DRUM) and are accessible viahttps://hdl.handle.net/11299/282667.

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

PY-OLF-D6PY00788K-s001
PY-OLF-D6PY00788K-s001.pdf (5.4MB, pdf)

Data Availability Statement

The data supporting this article has been included as part of the supplementary information (SI). Supplementary information: supplemental data, experimental details, characterization data, and supporting figures and tables. See DOI: https://doi.org/10.1039/d6py00788k.

The primary data files are archived with the Data Repository for the University of Minnesota (DRUM) and are accessible viahttps://hdl.handle.net/11299/282667.

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