{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,27]],"date-time":"2026-03-27T18:17:56Z","timestamp":1774635476514,"version":"3.50.1"},"reference-count":57,"publisher":"Wiley","issue":"5","license":[{"start":{"date-parts":[[2026,3,2]],"date-time":"2026-03-02T00:00:00Z","timestamp":1772409600000},"content-version":"vor","delay-in-days":1,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,3,1]],"date-time":"2026-03-01T00:00:00Z","timestamp":1772323200000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/100000964","name":"Arthritis National Research Foundation","doi-asserted-by":"publisher","award":["SRG\/2020\/001486"],"award-info":[{"award-number":["SRG\/2020\/001486"]}],"id":[{"id":"10.13039\/100000964","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["aces.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2026,3]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Chiral photoswitchable architectures represent a frontier in molecular science, offering platforms where light can precisely control both molecular conformation and stereochemical environment. While promising, integrating photoswitches into robust 3D scaffolds to achieve superior thermal stability and functional responsiveness remains challenging. Here, we report the rational design and synthesis of an azobenzene\u2010containing BINOL\u2010derived chiral dialdehyde that undergoes Dynamic Covalent Chemistry to form a discrete macrocycle with a bisamine and a novel cage with a trisamine. We conducted a systematic, comparative study across the three systems to isolate the effect of increasing structural confinement on photo\u2010switching characteristics. All three architectures\u2014the aldehyde, macrocycle, and cage\u2014exhibit reversible\n                    <jats:italic>E<\/jats:italic>\n                    \u2194\n                    <jats:italic>Z<\/jats:italic>\n                    photoisomerization of the azobenzene units under alternate irradiation with 370 and 456\u00a0nm light. In both the macrocycle and cage, the azobenzene units isomerize sequentially in both directions. Notably, both macrocyclization and cage formation significantly enhance photoswitching efficiency and substantially improve the thermal stability of the metastable\n                    <jats:italic>Z<\/jats:italic>\n                    \u2010isomer, a crucial requirement for practical applications. Furthermore, the cage exhibits pronounced light\u2010induced cavity modulation, resulting in significant shifts in its Circular Dichroism spectrum. These results establish molecular architecture as a crucial design principle for constructing highly responsive chiral hosts with tunable optical and structural features.\n                  <\/jats:p>","DOI":"10.1002\/asia.70655","type":"journal-article","created":{"date-parts":[[2026,3,8]],"date-time":"2026-03-08T19:26:35Z","timestamp":1772997995000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Architectural Control in Chiral Azobenzene Systems: Effects of Macrocycle and Cage Formation on Photoswitching Efficiency, Thermal Stability, and Chiroptical Properties"],"prefix":"10.1002","volume":"21","author":[{"given":"Diptiprava","family":"Sahoo","sequence":"first","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER\u2010TVM)  Thiruvananthapuram India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ritisha","family":"Srimany","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER\u2010TVM)  Thiruvananthapuram India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alex P.","family":"Andrews","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER\u2010TVM)  Thiruvananthapuram India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Soumen","family":"De","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER\u2010TVM)  Thiruvananthapuram India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2026,3,2]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557\u2010023\u201001387\u20108"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/cplu.202300353"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/cptc.202300126"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.200076"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.8.119"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.4c13010"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/poc.4599"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2SC05975D"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570\u2010021\u201000334\u2010w"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CP01873F"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268976.2021.1966113"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9PY00001A"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8QM00035B"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.molstruc.2017.09.108"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202401737"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.15.266"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.2c00549"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202003926"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200500682"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/cplu.202100322"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9900228"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c04846"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1038\/s44160\u2010022\u201000157\u20107"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2022.03.015"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929\u2010020\u20100452\u2010y"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC01891C"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.analchem.5c02384"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr050005k"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5CS00125K"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja413063e"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202216600"},{"key":"e_1_2_9_33_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202300092"},{"key":"e_1_2_9_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol203053q"},{"key":"e_1_2_9_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo201578z"},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0cc02685a"},{"key":"e_1_2_9_37_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202407034"},{"key":"e_1_2_9_38_1","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.18.53"},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC01507A"},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC05343A"},{"key":"e_1_2_9_41_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC01174G"},{"key":"e_1_2_9_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar500037v"},{"key":"e_1_2_9_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cs60044k"},{"key":"e_1_2_9_44_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs15305j"},{"key":"e_1_2_9_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201900163"},{"key":"e_1_2_9_46_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202214495"},{"key":"e_1_2_9_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202212745"},{"key":"e_1_2_9_48_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202015597"},{"key":"e_1_2_9_49_1","doi-asserted-by":"publisher","DOI":"10.1002\/open.202400400"},{"key":"e_1_2_9_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202404771"},{"key":"e_1_2_9_51_1","doi-asserted-by":"publisher","DOI":"10.1002\/chir.20828"},{"key":"e_1_2_9_52_1","doi-asserted-by":"publisher","DOI":"10.1055\/a-2637-5758"},{"key":"e_1_2_9_53_1","unstructured":"All the NMR studies are done in CDCl3 as it was cost effective while all other UV and CD spectroscopic studies were done in DCM solvent as chloroform UV cut off will not allow for the measurement of absorption of BINOL which is crutial for our studies."},{"key":"e_1_2_9_54_1","unstructured":"As methanol was one of the solvents for the crystallisation aldehyde moiety transforms to acetal during crystallisation."},{"key":"e_1_2_9_55_1","doi-asserted-by":"publisher","DOI":"10.1039\/b515476f"},{"key":"e_1_2_9_56_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja990326b"},{"key":"e_1_2_9_57_1","unstructured":"Direct1H NMR verification of imine stability at the concentrations used for UV\u2013vis and CD measurements (\u223c10\u22125M) is experimentally impractical due to insufficient signal\u2010to\u2010noise ratios and the equilibrium nature of imine formation which leads to a significant fraction of unreacted species At higher concentrations (>10\u00a0mM) oligomerization or polymerization is observed Stability assessments were therefore performed at intermediate concentrations where the assemblies are well\u2010defined and were found to be stable over the timescales relevant to the photophysical experiments."},{"key":"e_1_2_9_58_1","unstructured":"Although trends consistent with the elevated\u2010temperature studies were observed prolonged measurements led to gradual degradation and NMR line broadening due to the limited solution stability of the imine\u2010based assemblies precluding reliable quantitative analysis Thermal kinetics were therefore primarily evaluated at elevated temperatures to ensure experimental reliability."}],"container-title":["Chemistry \u2013 An Asian 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