{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T18:58:15Z","timestamp":1791226695697,"version":"4.1.0"},"reference-count":69,"publisher":"Wiley","issue":"41","license":[{"start":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T00:00:00Z","timestamp":1786924800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T00:00:00Z","timestamp":1786924800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/V049003\/1"],"award-info":[{"award-number":["EP\/V049003\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/X028208\/1"],"award-info":[{"award-number":["EP\/X028208\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000288","name":"Royal Society","doi-asserted-by":"publisher","award":["RSG\u2216R1\u2216180101"],"award-info":[{"award-number":["RSG\u2216R1\u2216180101"]}],"id":[{"id":"10.13039\/501100000288","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,10,5]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The one\u2010pot synthesis of apolar\u2010polar block copolymers combining polyolefins with polyesters has been a long\u2010standing challenge in polymer chemistry. Despite broad\u2010reaching applications of apolar\u2010polar block copolymers in drug delivery, compatibilisation of polymer blends and biomedical materials, their synthesis often requires multi\u2010step protocols with multiple catalysts and several isolation and purification steps. This is a particular challenge when combining the polymerisation of non\u2010activated \u03b1\u2010olefins with lactones, as these two distinct polymerisation mechanisms are often incompatible. This work reports heterobimetallic Janus catalysts for orthogonal 1\u2010hexene and \u03b5\u2010caprolactone polymerisation. Generated in situ, the active catalysts combine distinct Ti and Al metal centres connected by a Ti\u2010C(H)\u2550C(R)CH\n                    <jats:sub>2<\/jats:sub>\n                    O\u2010Al linker (R = Me or Bn). This approach successfully delivered poly(1\u2010hexene)\u2010\n                    <jats:italic>block<\/jats:italic>\n                    \u2010poly(\u03b5\u2010caprolactone) copolymers with well\u2010controlled linear block copolymer architectures, targeted molar compositions and tuneable molar mass (\n                    <jats:italic>M<\/jats:italic>\n                    <jats:sub>n<\/jats:sub>\n                    values &lt; 67.3\u00a0kDa,\n                    <jats:italic>\u00d0<\/jats:italic>\n                    = 1.47), in a one\u2010pot reaction, an approach that was successfully extended to poly(1\u2010octene)\u2010\n                    <jats:italic>block<\/jats:italic>\n                    \u2010poly(\u03b5\u2010caprolactone) and poly(1\u2010decene)\u2010\n                    <jats:italic>block<\/jats:italic>\n                    \u2010poly(\u03b5\u2010caprolactone) copolymers. Overall, this work is a notable addition to the toolbox for synthesising apolar\u2010polar block copolymers. This work demonstrates for the first time that titanium\u2010alkenyl complexes can efficiently initiate olefin polymerisations and that heterobimetallic complexes can act as efficient bifunctional initiators for distinct polymerisation mechanisms.\n                  <\/jats:p>","DOI":"10.1002\/anie.2602995","type":"journal-article","created":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T10:49:51Z","timestamp":1786963791000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Heterobimetallic Janus Catalysts for the One\u2010Pot Synthesis of Polar\u2010Apolar Block Copolymers"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9830-2888","authenticated-orcid":false,"given":"Raju","family":"Chambenahalli","sequence":"first","affiliation":[{"name":"School of Chemistry The University of Edinburgh  Edinburgh UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1597-3679","authenticated-orcid":false,"given":"Gary S.","family":"Nichol","sequence":"additional","affiliation":[{"name":"School of Chemistry The University of Edinburgh  Edinburgh UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9027-4931","authenticated-orcid":false,"given":"Jennifer A.","family":"Garden","sequence":"additional","affiliation":[{"name":"School of Chemistry The University of Edinburgh  Edinburgh UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,8,17]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202400443"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2262"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1093\/oso\/9780198506980.001.0001"},{"key":"e_1_2_8_5_1","first-page":"1","article-title":"Polymer Blends Handbook","author":"Utracki L. A.","year":"2014","journal-title":"Polymer Blends Handbook"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00426"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b03226"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0PY01534B"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ma00045a045"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/om1009395"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/om400925a"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9NJ05081G"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201104011"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2SC02265F"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.1c00557"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ma102329p"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.macromol.9b02602"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ma000679r"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ma50003a003"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00189"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.progpolymsci.2007.01.004"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.macromol.8b02475"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/macp.1997.021980502"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5CY00170F"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2021.213802"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00225"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500370f"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr990251u"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900079r"},{"key":"e_1_2_8_30_1","first-page":"14","volume-title":"CRC Handbook of Chemistry and Physics","author":"Lide D. R.","year":"1999"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1387\u20107003(00)00151\u20109"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/B105492A"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic010210s"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b00974"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/om049630q"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0277\u20105387(00)80665\u20108"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0020\u20101693(02)01306\u20103"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.macromol.3c00579"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/om9001389"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4DT00975D"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/om980955e"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0161857"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja036289c"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/om0493661"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521\u20103757(20010803)113:15<3002::AID\u2010ANGE3002>3.0.CO;2\u2010B"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar900030a"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr100294r"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1002\/jbm.a.31295"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8PY00649K"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/1099\u20100518(20001115)38:22<4095::AID\u2010POLA100>3.0.CO;2\u2010R"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c10588"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00310a100"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1039\/C39920000185"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0065\u20103055(08)60482\u20107"},{"key":"e_1_2_8_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9804691"},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1039\/B307365C"},{"key":"e_1_2_8_57_1","doi-asserted-by":"publisher","DOI":"10.1002\/macp.200290043"},{"key":"e_1_2_8_58_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CS00048B"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201003493"},{"key":"e_1_2_8_60_1","doi-asserted-by":"publisher","DOI":"10.1088\/1468\u20106996\/9\/2\/024402"},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apsusc.2016.04.034"},{"key":"e_1_2_8_62_1","doi-asserted-by":"publisher","DOI":"10.1002\/pol.1963.100010214"},{"key":"e_1_2_8_63_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.progpolymsci.2010.04.002"},{"key":"e_1_2_8_64_1","volume-title":"Comprehensive Organometallic Chemistry IV","author":"Parkin G.","year":"2022"},{"key":"e_1_2_8_65_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c02038"},{"key":"e_1_2_8_66_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.2c00364"},{"key":"e_1_2_8_67_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0760067"},{"key":"e_1_2_8_68_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c12310"},{"key":"e_1_2_8_69_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1381\u20101169(97)00179\u20109"},{"key":"e_1_2_8_70_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0005338"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.2602995","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.2602995","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.2602995","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T18:48:35Z","timestamp":1791226115000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.2602995"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,17]]},"references-count":69,"journal-issue":{"issue":"41","published-print":{"date-parts":[[2026,10,5]]}},"alternative-id":["10.1002\/anie.2602995"],"URL":"https:\/\/doi.org\/10.1002\/anie.2602995","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,17]]},"assertion":[{"value":"2026-06-07","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-07-28","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-08-17","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e2602995"}}