{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,24]],"date-time":"2026-04-24T23:56:17Z","timestamp":1777074977088,"version":"3.51.4"},"reference-count":66,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2021,8,5]],"date-time":"2021-08-05T00:00:00Z","timestamp":1628121600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemSusChem"],"published-print":{"date-parts":[[2021,9,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Solution\u2010based syntheses are omnipresent in chemistry but are often associated with obvious disadvantages, and the search for new mild and green synthetic methods continues to be a hot topic. Here, comparative studies in four different reaction media were conducted, that is, the solid\u2010state mechano\u2010 and slow\u2010chemistry synthesis, melted phase, and solution protocols, and the impact of the employed solvent\u2010free solid\u2010state versus liquid\u2010phase synthetic approaches was highlighted on a pool of products. A moderately exothermic model reaction system was chosen based on bis(pentafluorophenyl)zinc, (C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub>Zn, and 2,2,6,6\u2010tetramethylpiperidinyl oxide (TEMPO) as a stable nitroxyl radical, anticipating that these reagents may offer a unique landscape for addressing kinetic and thermodynamic aspects of wet and solvent\u2010free solid\u2010state processes. In a toluene solution two distinct paramagnetic Lewis acid\u2010base adducts (C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub>Zn(<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>\u2010TEMPO) (<jats:bold>1<\/jats:bold>) and (C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub>Zn(<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>\u2010TEMPO)<jats:sub>2<\/jats:sub> (<jats:bold>2<\/jats:bold>) equilibrated, but only <jats:bold>2<\/jats:bold> was affordable by crystallization. In turn, crystallization from the melt was the only method yielding single crystals of <jats:bold>1<\/jats:bold>. Moreover, the solid\u2010state approaches were stoichiometry sensitive and allowed for the selective synthesis of both adducts by simple stoichiometric control over the substrates. Density functional theory (DFT) calculations were carried out to examine selected structural and thermodynamic features of the adducts <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold>. Compound <jats:bold>2<\/jats:bold> is a unique non\u2010redox active metal complex supported by two nitroxide radicals, and the magnetic studies revealed weak\u2010to\u2010moderate intramolecular antiferromagnetic interactions between the two coordinated TEMPO molecules.<\/jats:p>","DOI":"10.1002\/cssc.202101269","type":"journal-article","created":{"date-parts":[[2021,7,20]],"date-time":"2021-07-20T11:23:14Z","timestamp":1626780194000},"page":"3887-3894","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["A Case Study on the Desired Selectivity in Solid\u2010State Mechano\u2010 and Slow\u2010Chemistry, Melt, and Solution Methodologies"],"prefix":"10.1002","volume":"14","author":[{"given":"Krzysztof","family":"Budny\u2010Godlewski","sequence":"first","affiliation":[{"name":"Faculty of Chemistry Warsaw University of Technology  Noakowskiego 3 00-664 Warsaw Poland"},{"name":"Institute of Physical Chemistry Polish Academy of Sciences  Kasprzaka 44\/52 01-224 Warsaw Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Micha\u0142 K.","family":"Leszczy\u0144ski","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Warsaw University of Technology  Noakowskiego 3 00-664 Warsaw Poland"},{"name":"Institute of Physical Chemistry Polish Academy of Sciences  Kasprzaka 44\/52 01-224 Warsaw Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Adam","family":"Tulewicz","sequence":"additional","affiliation":[{"name":"Institute of Physical Chemistry Polish Academy of Sciences  Kasprzaka 44\/52 01-224 Warsaw Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Iwona","family":"Justyniak","sequence":"additional","affiliation":[{"name":"Institute of Physical Chemistry Polish Academy of Sciences  Kasprzaka 44\/52 01-224 Warsaw Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dawid","family":"Pinkowicz","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Jagiellonian University  Gronostajowa 2 30-387 Cracow Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Barbara","family":"Sieklucka","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Jagiellonian University  Gronostajowa 2 30-387 Cracow Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Krzysztof","family":"Krucza\u0142a","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Jagiellonian University  Gronostajowa 2 30-387 Cracow Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zbigniew","family":"Sojka","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Jagiellonian University  Gronostajowa 2 30-387 Cracow Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Janusz","family":"Lewi\u0144ski","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Warsaw University of Technology  Noakowskiego 3 00-664 Warsaw Poland"},{"name":"Institute of Physical Chemistry Polish Academy of Sciences  Kasprzaka 44\/52 01-224 Warsaw Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2021,8,5]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1098\/rsos.191378"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00479"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-020-00249-y"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/C1CS15171A"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs35442j"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.6b00277"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1038\/524020a"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0GC02264K"},{"key":"e_1_2_7_9_1","unstructured":"We view the term slow chemistry as a historically and heuristically useful categorization of solid-state transformations between two distinct solid substrates with kinetics limited by diffusion which occur at ambient temperature without an external stimuli. We think that this term even if derivative is a good way to distinguish from an aging or temperature-solvent-and vapor\u2013mediated solid\u2013state reactions."},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cs60052a"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7SC05371A"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT03866A"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS00813A"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.9b00454"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.mattod.2021.01.008"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/nmat4732"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/b709411f"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0034388"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CE00440E"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2gc36005e"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.molliq.2015.12.015"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2006.10.046"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2SC20344H"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201106715"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201106715"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3gc40520f"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/C3GC41370E"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules22010144"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201200236"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.9b04552"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9SC01396B"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(03)00554-4"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1139\/v98-064"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-2008-1078445"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b05001"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr010303r"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2014.10.012"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2020.213611"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20000901)6:17<3215::AID-CHEM3215>3.0.CO;2-8"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200601001"},{"key":"e_1_2_7_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200601001"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200803254"},{"key":"e_1_2_7_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200803254"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200902716"},{"key":"e_1_2_7_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200902716"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201101997"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201904380"},{"key":"e_1_2_7_43_2","doi-asserted-by":"crossref","first-page":"8614","DOI":"10.1002\/ange.201904380","volume":"131","year":"2019","journal-title":"Angew. 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