{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T17:01:33Z","timestamp":1791133293621,"version":"4.1.0"},"reference-count":120,"publisher":"Wiley","issue":"33","license":[{"start":{"date-parts":[[2010,7,23]],"date-time":"2010-07-23T00:00:00Z","timestamp":1279843200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2010,9,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>2,6\u2010Bis(1,2,3\u2010triazol\u20104\u2010yl)pyridine (btp) ligands with substitution patterns ranging from strongly electron\u2010donating to strongly electron\u2010accepting groups, readily prepared by means of Cu\u2010catalyzed 1,3\u2010dipolar cycloaddition (the \u201cclick\u201d reaction), were investigated with regard to their complexation behavior, and the properties of the resulting transition\u2010metal compounds were compared. Metal\u2013btp complexes of 1:1 stoichiometry, that is, [Ru(btp)Cl<jats:sub>2<\/jats:sub>(dmso)] and [Zn(btp)Br<jats:sub>2<\/jats:sub>], could be isolated and were crystallographically characterized: they display octahedral and trigonal\u2010bipyramidal coordination geometries, respectively, and exhibit high aggregation tendencies due to efficient \u03c0\u2013\u03c0 stacking leading to low solubilities. Metal\u2013btp complexes of 1:2 stoichiometry, that is, [Fe(btp)<jats:sub>2<\/jats:sub>]<jats:sup>2+<\/jats:sup> and [Ru(btp)<jats:sub>2<\/jats:sub>]<jats:sup>2+<\/jats:sup>, could also be synthesized and their metal centers show the expected octahedral coordination spheres. The iron compounds exhibit quite a complex magnetic behavior in the solid state including spin crossover near room temperature, and hysteresis and locking into high\u2010spin states on tempering at 400\u2005K, depending on the substituents on the btp ligands. Cyclic voltammetry studies of [Ru(btp)<jats:sub>2<\/jats:sub>]<jats:sup>2+<\/jats:sup> reveal strong modulation of the oxidation potentials by more than 0.6\u2005V and a clear linear correlation to the Hammett constant (<jats:italic>\u03c3<jats:sub>para<\/jats:sub><\/jats:italic>) of the substituent at the pyridine core. Isothermal titration calorimetry was used to measure the thermodynamics of the Fe<jats:sup>II<\/jats:sup>\u2013btp complexation process and enabled accurate determination of the complexation enthalpies, which display a linear relationship with the <jats:italic>\u03c3<jats:sub>para<\/jats:sub><\/jats:italic> values for the terminal phenyl substituents. Detailed NMR spectroscopic studies finally revealed that in the case of Fe<jats:sup>II<\/jats:sup> complexation, dynamics are rapid for all investigated btp derivatives in acetonitrile, while replacing Fe<jats:sup>II<\/jats:sup> by Ru<jats:sup>II<\/jats:sup> or changing the solvent to dichloromethane effectively slows down ligand exchange. The results nicely demonstrate the utility of substituent parameters, originally developed for linear free\u2010energy relationships to explain reactivity in organic reactions, in coordination chemistry, and to illustrate the potential to custom\u2010design btp ligands and complexes thereof with predictable properties. The fast equilibration of the [Fe(btp)<jats:sub>2<\/jats:sub>]<jats:sup>2+<\/jats:sup> complexes together with their tunable stability and interesting magnetic properties should enable the design of dynamic metallosupramolecular materials with advantageous properties.<\/jats:p>","DOI":"10.1002\/chem.201000721","type":"journal-article","created":{"date-parts":[[2010,7,23]],"date-time":"2010-07-23T11:50:40Z","timestamp":1279885840000},"page":"10202-10213","source":"Crossref","is-referenced-by-count":102,"title":["Complexes of Click\u2010Derived Bistriazolylpyridines: Remarkable Electronic Influence of Remote Substituents on Thermodynamic Stability as well as Electronic and Magnetic Properties"],"prefix":"10.1002","volume":"16","author":[{"given":"Marc","family":"Ostermeier","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marie\u2010Anne","family":"Berlin","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Robert\u2005M.","family":"Meudtner","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Serhiy","family":"Demeshko","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Franc","family":"Meyer","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christian","family":"Limberg","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stefan","family":"Hecht","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2010,8,26]]},"reference":[{"key":"e_1_2_5_1_2","unstructured":"Original work:"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/jr9320000020"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527608486"},{"key":"e_1_2_5_4_2","unstructured":"Original work:"},{"key":"e_1_2_5_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00105a047"},{"key":"e_1_2_5_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020004h"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2005.03.010"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr941154y"},{"key":"e_1_2_5_9_2","unstructured":"Reviews are given in:"},{"key":"e_1_2_5_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200602205"},{"key":"e_1_2_5_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200602205"},{"key":"e_1_2_5_11_2","volume-title":"Molecular Magnetism","author":"Kahn O.","year":"1993"},{"key":"e_1_2_5_12_2","unstructured":"Reviews are given in:"},{"key":"e_1_2_5_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0957-4166(97)00593-4"},{"key":"e_1_2_5_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar960062n"},{"key":"e_1_2_5_15_2","unstructured":"The term \u201cclick chemistry\u201d usually refers to the Cu\u2010catalyzed 1 3\u2010dipolar cycloaddition reaction pioneered by:"},{"key":"e_1_2_5_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020715)114:14<2708::AID-ANGE2708>3.0.CO;2-0"},{"key":"e_1_2_5_16_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020715)41:14<2596::AID-ANIE2596>3.0.CO;2-4"},{"key":"e_1_2_5_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo011148j"},{"key":"e_1_2_5_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0783479"},{"key":"e_1_2_5_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010601)113:11<2056::AID-ANGE2056>3.0.CO;2-W"},{"key":"e_1_2_5_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5"},{"key":"e_1_2_5_20_2","unstructured":"\u00a0"},{"key":"e_1_2_5_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701240"},{"key":"e_1_2_5_22_2","first-page":"261","volume":"50","author":"Berlin M.\u2010A.","year":"2009","journal-title":"Polym. 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These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_5_42_2","unstructured":"\u00a0"},{"key":"e_1_2_5_43_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.200400330"},{"key":"e_1_2_5_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic049822d"},{"key":"e_1_2_5_45_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9840001349"},{"key":"e_1_2_5_46_2","unstructured":"\u00a0"},{"key":"e_1_2_5_47_2","doi-asserted-by":"publisher","DOI":"10.1039\/jr9560000594"},{"key":"e_1_2_5_48_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0365110X66002147"},{"key":"e_1_2_5_49_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270183005466"},{"key":"e_1_2_5_50_2","doi-asserted-by":"publisher","DOI":"10.1039\/b003010o"},{"key":"e_1_2_5_51_2","unstructured":"The distances between the carbon atoms binding the hydrogen atoms which are considered to be responsible for the hydrogen bonds and the halogen atoms are comparable to the sum of the van der Waals (vdW) radii of the halogen and carbon atoms: \u2211[rvdW(Cl) rvdW(C)]=3.5\u2005\u00c5 distances Cl\uf8ffC found in the crystal structure of [Ru(3\u2009c)Cl2(dmso)]=3.5\u2005\u00c5; \u2211[rvdW(Br) rvdW(C)]=3.6\u2005\u00c5 distances Br\uf8ffC found in the crystal structure of [Zn(1\u2009a)Br2]=3.6\u20133.7\u2005\u00c5."},{"key":"e_1_2_5_52_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(93)83132-F"},{"key":"e_1_2_5_53_2","unstructured":"\u00a0"},{"key":"e_1_2_5_54_2","unstructured":"A similar strategy has been applied before for the synthesis of [RuL2]2+complexes withLrepresenting\u2014for instance\u2014tripodal phosphane ligands."},{"key":"e_1_2_5_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00277a008"},{"key":"e_1_2_5_56_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19941062006"},{"key":"e_1_2_5_56_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199420241"},{"key":"e_1_2_5_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.19960020915"},{"key":"e_1_2_5_58_2","doi-asserted-by":"publisher","DOI":"10.1039\/b100995h"},{"key":"e_1_2_5_59_2","doi-asserted-by":"publisher","DOI":"10.1039\/b108468m"},{"key":"e_1_2_5_60_2","doi-asserted-by":"publisher","DOI":"10.1039\/B502175H"},{"key":"e_1_2_5_61_2","doi-asserted-by":"publisher","DOI":"10.1039\/B510370C"},{"key":"e_1_2_5_62_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-1902(66)80196-3"},{"key":"e_1_2_5_62_3","doi-asserted-by":"publisher","DOI":"10.1063\/1.1725133"},{"key":"e_1_2_5_63_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200500316"},{"key":"e_1_2_5_63_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200500316"},{"key":"e_1_2_5_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00331a030"},{"key":"e_1_2_5_65_2","unstructured":"\u00a0"},{"key":"e_1_2_5_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01280a022"},{"key":"e_1_2_5_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00002a004"},{"key":"e_1_2_5_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr60165a003"},{"key":"e_1_2_5_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic7016769"},{"key":"e_1_2_5_70_2","doi-asserted-by":"publisher","DOI":"10.1039\/b819812h"},{"key":"e_1_2_5_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic702428s"},{"key":"e_1_2_5_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/om7009057"},{"key":"e_1_2_5_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/om020147u"},{"key":"e_1_2_5_74_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2005.12.065"},{"key":"e_1_2_5_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm00269a003"},{"key":"e_1_2_5_76_2","unstructured":"Even though the complex derived from ligand1\u2009bcarries terminal methyl groups instead of iodine substituents it nicely matches the linear fit thus illustrating the dominant role of the central pyridine moiety (vide infra)."},{"key":"e_1_2_5_77_2","unstructured":"\u00a0"},{"key":"e_1_2_5_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic000113j"},{"key":"e_1_2_5_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic001457c"},{"key":"e_1_2_5_80_2","unstructured":"\u00a0"},{"key":"e_1_2_5_81_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-1352(199901\/02)12:1<3::AID-JMR441>3.0.CO;2-6"},{"key":"e_1_2_5_82_2","doi-asserted-by":"publisher","DOI":"10.1021\/ac00217a002"},{"key":"e_1_2_5_83_2","doi-asserted-by":"publisher","DOI":"10.1039\/a802370k"},{"key":"e_1_2_5_84_2","doi-asserted-by":"publisher","DOI":"10.3390\/ijms10072935"},{"key":"e_1_2_5_85_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.drudis.2008.06.004"},{"key":"e_1_2_5_86_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0304-4157(00)00009-5"},{"key":"e_1_2_5_87_2","doi-asserted-by":"publisher","DOI":"10.3390\/ijms10083283"},{"key":"e_1_2_5_88_2","doi-asserted-by":"publisher","DOI":"10.3390\/ijms10083457"},{"key":"e_1_2_5_89_2","unstructured":"\u00a0"},{"key":"e_1_2_5_90_2","doi-asserted-by":"publisher","DOI":"10.1021\/bk-2006-0928.ch004"},{"key":"e_1_2_5_91_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma047737j"},{"key":"e_1_2_5_92_2","unstructured":"\u03c0\u2010Conjugation through 1 4\u2010connected 1 2 3\u2010triazole units has been suggested by the work on triazole\u2010containing main\u2010chain polymers see:"},{"key":"e_1_2_5_93_2","doi-asserted-by":"publisher","DOI":"10.1039\/b507776a"},{"key":"e_1_2_5_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma0615912"},{"key":"e_1_2_5_95_2","unstructured":"\u00a0"},{"key":"e_1_2_5_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50174a031"},{"key":"e_1_2_5_97_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01277625"},{"key":"e_1_2_5_98_2","unstructured":"For a related assignment of absorption bands in the course of [Fe(tpy)2]2+formation see reference\u2005[36a]."},{"key":"e_1_2_5_99_2","unstructured":"\u00a0"},{"key":"e_1_2_5_100_2","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1968-0801"},{"key":"e_1_2_5_101_2","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1968-0802"},{"key":"e_1_2_5_102_2","doi-asserted-by":"crossref","first-page":"1349","DOI":"10.1515\/znb-1972-1113","volume":"27","author":"Mauser H.","year":"1968","journal-title":"Z. 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However the complexation\u2010induced large shifts antagonize the resolution of averaged signals into separate ones (unlike in case of the proton signals within the high\u2010field region) since the increased chemical\u2010shift difference results in a lowered coalescence temperature and hence increased signal widths. Therefore the differentiation between free and complexed btp is not possible at 243\u2005K."},{"key":"e_1_2_5_110_2","unstructured":"Note that ESI\/MS spectra of the corresponding Ru complex mainly show the expected peaks for [Ru(1\u2009b)2]2+(Figure\u200543 in the Supporting Information)."},{"key":"e_1_2_5_111_2","unstructured":"\u00a0"},{"key":"e_1_2_5_112_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0000978"},{"key":"e_1_2_5_113_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr990126i"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201000721","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201000721","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T15:13:54Z","timestamp":1760282034000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201000721"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2010,8,26]]},"references-count":120,"journal-issue":{"issue":"33","published-print":{"date-parts":[[2010,9,3]]}},"alternative-id":["10.1002\/chem.201000721"],"URL":"https:\/\/doi.org\/10.1002\/chem.201000721","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2010,8,26]]}}}