{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,9,19]],"date-time":"2025-09-19T07:35:52Z","timestamp":1758267352594},"reference-count":71,"publisher":"Wiley","issue":"10","license":[{"start":{"date-parts":[[2004,10,21]],"date-time":"2004-10-21T00:00:00Z","timestamp":1098316800000},"content-version":"vor","delay-in-days":20,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Helvetica Chimica Acta"],"published-print":{"date-parts":[[2004,10]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The new tetraazamacrocycle <jats:bold>2<\/jats:bold> (=2,2\u2032\u2010[[7\u2010Methyl\u20103,7,11,17\u2010tetraazabicyclo[11.3.1]heptadeca\u20101(17),13,15\u2010triene\u20103,11\u2010diyl]bis(methylene)]bis(4\u2010bromophenol)) was synthesized and used as a ligand for different metal\u2010ion complexes. The X\u2010ray crystal structures of the complexes of the general formula [M(H\u2010<jats:bold>2<\/jats:bold>)]<jats:sup>+<\/jats:sup>NO<jats:styled-content>$\\rm{_{3}^{-}}$<\/jats:styled-content>\u22c5MeOH (M=Ni<jats:sup>2+<\/jats:sup>, Zn<jats:sup>2+<\/jats:sup>), in which only one of the two pendant phenolic OH groups of <jats:bold>2<\/jats:bold> is deprotonated, were determined. In both complexes, the coordination environment is of the [5+1] type, the four N\u2010atoms of the macrocyclic framework defining a square\u2010planar arrangement around the metal center, with similar Ni\uf8ffN and Zn\uf8ffN distances of 1.961(9) to 2.157(9)\u2005\u00c5 and 2.021(9) to 2.284(8)\u2005\u00c5, respectively. In contrast, the M\uf8ffO distances are markedly different, 2.060(6) and 2.449(8)\u2005\u00c5 in the Ni<jats:sup>II<\/jats:sup> complex, and 2.027(7) and 2.941(9)\u2005\u00c5 in the Zn<jats:sup>II<\/jats:sup> complex. The UV\/VIS spectra of the Ni<jats:sup>II<\/jats:sup> and Cu<jats:sup>II<\/jats:sup> complexes with ligand <jats:bold>2<\/jats:bold>, and the EPR spectra of the Cu<jats:sup>II<\/jats:sup> system, suggest the same type of structure for the complexes in solution as in the solid state. Theoretical studies by means of density functional theory (DFT) confirmed the experimental structures of the Ni<jats:sup>II<\/jats:sup> and Zn<jats:sup>II<\/jats:sup> complexes, and led to a proposal of a similar structure for the corresponding Cu<jats:sup>II<\/jats:sup> complex. The calculated EPR parameters for the latter and comparison with related data support this interpretation. The singly occupied molecular orbital (SOMO) in these systems is mainly made of a d orbital of Cu, with a strong antibonding (<jats:italic>\u03c3<\/jats:italic>*) contribution of the axially bound phenolate residue.<\/jats:p>","DOI":"10.1002\/hlca.200490235","type":"journal-article","created":{"date-parts":[[2004,10,21]],"date-time":"2004-10-21T16:05:04Z","timestamp":1098374704000},"page":"2613-2628","source":"Crossref","is-referenced-by-count":4,"title":["Structure, Characterization, and Metal\u2010Complexation Properties of a New Tetraazamacrocycle Containing Two Phenolic Pendant Arms"],"prefix":"10.1002","volume":"87","author":[{"given":"Xiuling","family":"Cui","sequence":"first","affiliation":[]},{"given":"Maria\u2005Jos\u00e9","family":"Calhorda","sequence":"additional","affiliation":[]},{"given":"Paulo\u2005J.","family":"Costa","sequence":"additional","affiliation":[]},{"given":"Rita","family":"Delgado","sequence":"additional","affiliation":[]},{"given":"Michael\u2005G.\u2005B.","family":"Drew","sequence":"additional","affiliation":[]},{"given":"V\u00edtor","family":"F\u00e9lix","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,10,21]]},"reference":[{"key":"e_1_2_1_1_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(97)00003-9"},{"key":"e_1_2_1_1_3","first-page":"65","volume":"3","author":"Kaden T. 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