Selective control of donor-acceptor Stenhouse adduct populations with non-selective stimuli

•Thermal isomerization pathways of donor-acceptor Stenhouse adducts are tuned by polarity•Non-selective stimuli produce selective responses in the DASA mixture Natural systems such as cells or organisms consist thousands stimulus-responsive and adaptive molecules assemblies enzymes proteins. To achieve a multitude selectivity despite limited set available stimuli, nature relies on highly controlled shallow multi-step energy landscapes. The development small with multi-responsive reaction provides an opportunity to multiple outcomes through same stimuli. Such properties promise more complex even life-like responsive materials. This work showcases how pathway (DASAs) can be utilized program derivatives similar architectures respond differently change their landscape non-selective Multifaceted material upon exposure key for developing Developing synthetic systems, though not trivial, typically orthogonal enable control molecular that behavior. Access tunable mechanisms diverse landscapes offers alternative strategy controlling out-of-equilibrium processes without requiring each unit. Donor-acceptor class photoswitches have complex, tunable, environmentally sensitive pathways. We present adduct equilibrium photoswitching kinetics changes polarity environment. Polarity light used selectively three where response comes from is driven given paves way designing self-regulating ability adapt environmental chemical signals fundamental biological processes. Numerous naturally occurring activation proteins signal cascades,1Wu H. Higher-order new paradigm transduction.Cell. 2013; 153: 287-292https://doi.org/10.1016/j.cell.2013.03.013Abstract Full Text PDF PubMed Scopus (244) Google Scholar rely innate convert cues into tightly structural responses, reconfigurations, movements. As our understanding these continues grow, field “smart,” materials capable mimicking nature’s dynamic also expand. 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Adv. 8: eadd1980https://doi.org/10.1126/sciadv.add1980Crossref envisioned effect independent populations includes barriers close energy. this mechanism, changes, which pathway, should generate driving separate parts landscape. investigate hypothesis, chose study commonly (DASA-1, DASA-2, DASA-3). These differences electronic donors acceptors, resulting ground-state charge separation, i.e., measured solvatochromic slope λmax ten solvents, negative indicates higher separation.29Sroda Previous al. quantum yield B largely difference surface.30Lerch solvation model based density (SMD) chloroform dielectric constant surface DASA-1, DASA-3. Structures were optimized M06-2X/6-31+G(d,p), previously give reasonable DASAs.19Zulfikri Single points calculated M06-2X/def2-QZVP. All calculations done Gaussian 16.33Frisch Trucks G.W. Schlegel H.B. Scuseria Cheeseman Scalmani Barone Petersson Nakatsuji al.Gaussian 16, revision C.01. Gaussian, 2016https://gaussian.com/citation/Google method was chosen its inexpensive cost performance compared those benchmarked (see supplemental section 4.1 details). double-bond character directly related transition-state barriers, forward (B-Bʹ-Cenol) backward (Cenol-Bʹ-B-A) (Figures 2A 2B). principle here barrier behaves opposite B-Bʹ Bʹ-Cenol bond alternation 2A, 2B, S4–S27). Upon polarity, C3–C4 decreases, leading decrease corresponding rotation (A B) 2 S7–S27). leads around C2–C3 bond, (B B′) subsequent 4π-electrocyclization proton transfer influenced distance C5 C1, farther increasingly polar likely vs. double bonds 2, S5, S6). trends all investigated DASA-3; Figures 3A, S6).Figure 3Difference structuresShow caption(A) structures respective slope.(B) Calculated M06-2X/def2-QZVP SMD(chloroform). Energy step. Values show highest after reactions recovery C: rate-determining back reactions, respectively.View Large Image Figure ViewerDownload Hi-res image Download (PPT) (A) slope. (B) respectively. Although appears fashion, experimentally kinetic properties.9Helmy Scholar,17Lerch determine source behavior, initial chloroform. DASA-1 consists dialkylamine strong electron-donating combined weakly withdrawing acceptor N,N′-dimethyl barbituric acid, −44 nm.27Stricker DASA-2 retains but replaces donating 2-methylindoline, charge-separated ground state -5 nm. DASA-3 weak (2-methylindoline) strongly CF3-pyrazolone acceptor. −60 nm 3A).29Sroda first important separation 3B). second stability isomer, Cenol, comparison Cenol stabilized (presumably gain aromatic pyrazalone form) might relatively destabilized isomer increased stabilization A, lost cyclization. faster closure lower cyclization well having therefore before recovery. Similarly, B′), regime environments. contrast, favored ring-closed isomers, Czwit Cketo, highlight electronics lead vastly inherent translate thermodynamics, time-dependent UV-visible (UV-vis) spectroscopy 1H-NMR 4). irradiated 530 dichloromethane (DCM) (ε = 8.9), 10% loss absorbance 564 100 s form. If acetonitrile (ACN, DCM; ε 37.5) added, slows down, smaller amount time. adding diethyl ether (Et2O, ε=4.3), DCM, slight forming 4B). down amounts ACN increase, whereas Et2O appear significantly kback (Table S4). data line expectation B′, decreased rate interconversion steps. confirmed observing population pump-probe spectroscopy. B, slightly under S37). Meanwhile, observed slowdown rates addition ACN, suggesting either Bʹ forms did calculate. Irradiation DCM 617 LED 4C). dark, two-magnitude slower S5) DASA-1. Et2O. recovery, increased. seems reflective fact high solely responsible kinetics. Monitoring via trend drop C-isomer generated time S38). when Et2O, reflecting reached 33% it 4D). Interestingly, percentage conjunction detect methods, observe regarding generation C-isomers. Increasing resulted C-isomers short time, C S39). suggests increases increases, although total longer periods simultaneous promising us influences ways, behaviors different. shuts decreases. Furthermore, stabilizers solvents S40) reversibly process additives S41 S42). deeply understand open- closed-from equilibria, monitored storing 24 h dueterated ethaonol (EtOD). closed-form isomers; zwitterionic Czwit, Cketo 2).11Hemmer EtOD, shifted 74% 35% 4F S50). hand, saw 38% 46% 4G S51). DASA-3, 100% 43% EtOD 4H S52). (Czwit) (Cketo) media.10Lerch held true deuterated dimethyl sulfoxide (DMSO-d6) well, seemed bonding ethanol, had stronger hydrogen-bonding abilities larger S1; 11). DMSO-d6 outsized presumably hydrogen-bond character. experience facto landscape, starting hybridization, drastically Each favors allowing accessed secondary chemistry. showcase opportunity, 5A–5C S60–S64) toluene. toluene minimal extended 5B, 5C, S61), good (with 5A–5C, S60, S62). start nonpolar environment, kinetics, DCM. additive large S1 S55). predicted, 15 vol % DMSO added toluene, distinct S60–S62). caused quickly thermally isomerize S62) now thermodynamically trapped reset while suppressing 5A S60). isomerized isomerization, light-induced shut B′. recover allowed S61). reacted enables behavior molecules. mixed, overlapping absorbances distinctive peaks 5A, S63). white (for details followed, see 13.3) converted 5C). After irradiation, recovered, remained only irradiation. could then switched repeatedly continued slow UV-vis measurement beam (recovery 1H-NMR; S74–S77). solution 5C), 6% value. Conversely, DASA-2. partially 5A). reversibly, kinetically Through stimulus, demonstrating list states, S73). generality repeated experiment (supplemental 13.2). Our potential distinguish believe pathway-discrimination will systems. impact computational experimental approach. switching. investigated, varies mixture. highlights multi-stimulus-responsive, surfaces. mimic found nature.